We present a new, novel implementation of the Many-Body Expansion (MBE) to account for the breaking of covalent bonds, thus extending the range of applications from its previous popular usage in the breaking of hydrogen bonds in clusters to molecules. A central concept of the new implementation is the in situ atomic electronic state of an atom in a molecule that casts the one-body term as the energy required to promote it to that state from its ground state. The rest of the terms correspond to the individual diatomic, triatomic, etc., fragments. Its application to the atomization energies of the XHn series, X = C, Si, Ge, Sn and n = 1–4, suggests that the (negative, stabilizing) 2-B is by far the largest term in the MBE with the higher order terms oscillating between positive and negative values and decreasing dramatically in size with increasing rank of the expansion. The analysis offers an alternative explanation for the purported “first row anomaly” in the incremental Hn−1X–H bond energies seen when these energies are evaluated with respect to the lowest energy among the states of the XHn molecules. Due to the “flipping” of the ground/first excited state between CH2 (3B1 ground state, 1A1 first excited state) and XH2, X = Si, Ge, Sn (1A1 ground state, 3B1 first excited state), the overall picture does not exhibit a “first row anomaly” when the incremental bond energies are evaluated with respect to the molecular states having the same in situ atomic states.
I. INTRODUCTION
The Many-Body Expansion (MBE) is a concept based on combinatorial mathematics that was first introduced over 300 years ago and is usually employed to count the number of elements in the union of finite sets.1 Its first application to chemical physics problems considered individual water molecules as “bodies” connected via hydrogen bonds as it was used to estimate the non-additive three-body term by partitioning the energy of a water trimer.2 Since then the MBE analysis based on the energies of distinct, non-overlapping sub-fragments has been applied to hydrogen bonded clusters by some of us3–9 and others10–27 to quantify the importance of non-additive terms in the binding energies of aqueous clusters. Recently, the details of the MBE based on high level electronic structure calculations related to the size of the orbital basis set and the level of electron correlation used in the expansion28–30 as well as a molecular dynamics protocol based on the MBE (MBE-MD)31 were reported. This type of MBE for hydrogen bonded molecular systems (including ions), where the definition of a “body” is straightforward and the system is partitioned in non-overlapping sub-fragments (monomers, dimers, trimers, etc.) by just breaking hydrogen bonds, has laid the foundation for the development of accurate, ab initio based, many-body interaction potentials for water.32–53 This is to be contrasted to different partitions that are, for instance, based on overlapping sub-fragments, such as the Molecular Tailoring Approach (MTA),54–59 or other fragmentation based approaches.60–64 Note that the MBE has also been applied to incorporate molecular orbitals as “bodies” in order to extrapolate the total correlation energy of molecules65–72 and solids.73–75
In this paper, we extend the general idea of the MBE to the breaking of covalent bonds, that is, considering a polyatomic molecule as consisting of a collection of atoms, diatomics, triatomics, etc. A recent study76 of the carbon, silicon, and germanium hydrides, XHn (n = 1–4) based on the spin-coupled generalized valence bond theory has examined the qualitative changes between carbon and silicon/germanium in the Hn−1X–H bond energies (De) on the context of the “first raw anomaly”77 by expanding on Kutzelnigg’s argument78 based on the hybridization of the X atom bond orbitals due to the increase in the spatial separation of the ns and np orbitals between atoms in the first row and the following rows of the Periodic Table. The results presented in our study offer (vide infra) an alternative explanation for this result.
Our analysis is based on casting the atomization energy (ΔEatomiz⋅) of a molecule of N atoms computed with respect to its constituent atoms i (i = 1, …, N) in their respective ground states () in the usual way4 as
where
and , , , , etc., are the energies of the in situ (ground or excited) states of atom (i), dimer (ij), trimer (ijk), tetramer (ijkl), etc., in the molecule. It is obvious that if the in situ state of an atom in the molecule () is the atom’s ground state (), the 1-B term for that atom, given by Eq. (2), is zero.
Since the concept of the in situ state of an atom in the molecule is central to our analysis, we will further discuss it using Fig. 1, as discussed by Heitler.79 Consider a carbon atom in its ground (3P) atomic state. The pairing of the four (2s22p2) valence electrons in this electronic state is not appropriate to accommodate bonding with four hydrogen atoms to form CH4. They should rather be promoted to the 5S excited electronic state lying 4.18 eV above80 the 3P ground state in order to form the 4 equivalent C–H bonds. In order words, the 2s and the three 2p orbitals of the carbon atom should be hybridized into four equivalent sp3 orbitals forming the atomic 5S state, which is the in situ electronic state of the carbon atom in CH4. Examples of the concept of in situ atomic states have been previously discussed for molecules81,82 and metal aqueous clusters.83,84 As it is evident from Eqs. (1)–(4), the choice of the in situ electronic state of an atom will affect the MBE.
II. METHODOLOGY
The calculations for the ground states of the XHn hydrides, X = C, Si, Ge, Sn and n = 1–4, were performed at the Coupled Cluster Singles, Doubles and perturbative Triples [CCSD(T) and RCCSD(T)]85,86 levels of theory. Additionally, two excited states for CH and one for the remaining diatomic and all triatomic molecules were computed. For the CHn series, we employed Dunning’s augmented correlation consistent basis sets, aug-cc-pVxZ, x = D, T, Q.87,88 For the SiHn, GeHn, and SnHn species, we employed the aug-cc-pVQZ basis sets for H,87,88 Si,89 and Ge,90 and for Sn Peterson’s91 aug-cc-pVQZ-PP augmented correlation consistent basis sets, which employ accurate small-core (1s22s22p63s23p63d10; 28 electrons) relativistic pseudopotentials.
The atomization energies, the XHn−1–H dissociation energies, and the individual many body terms were corrected for basis set superposition error (BSSE)92,93 as described in Ref. 94. Note that the deformation (or relaxation) energy in that reference that arises from geometrical distortions due to the interaction is zero in the present case since the atomization energy is computed with respect to the atoms. The BSSE-corrected interaction energies (ΔE′atomiz.) and the BSSE-corrected many-body terms, ΔE′(n-B), e given in Eqs. (5)–(10),4
etc., where refers to the total energy of the molecule M computed at the geometry G with basis set s.
In order to evaluate the appropriateness of RCCSD(T), which is a single-reference method, we checked the single (t1) and the double (t2) amplitudes95 as well as the T1 and D1 diagnostics.96,97 For all calculations of the present study, the t1 and t2 amplitudes were small and the T1 and D1 diagnostics were T1 < 0.02 and D1 < 0.04, expect for the 4Σ− state of XH, for which the diagnostics were T1 ∼ 0.03 and D1 ∼ 0.07. We can, therefore, conclude that the single reference RCCSD(T) method is an appropriate methodology to be employed for the systems in this study. All calculations were carried out with the MOLPRO suite of codes.98
An important detail of the above analysis is that, for each electronic state of the molecule, the two- and higher-body terms are not necessarily computed at the diatomic, triatomic, etc., ground electronic states but at the respective electronic states of these fragments that are formed from the in situ electronic states of the constituent atoms in the full molecule. We will further elaborate on this important detail in Sec. III when we present the case of XH2.
III. RESULTS AND DISCUSSION
A. The MBE for the XHn series (X = C, Si, Ge, Sn; n = 1–4)
The results in this subsection are presented in Figs. 2–13 and Tables I–V. Below we will discuss the individual members of the XHn series for each n as well as the trends with the atom identity.
Many-body decomposition of ΔEatomiz. for the 2Π, 4Σ−, and 2Δ states of CH at the RCCSD(T)/aug-cc-pVxZ, x = D, T, Q, level of theory.
Many-body decomposition of ΔEatomiz. for the 2Π, 4Σ−, and 2Δ states of CH at the RCCSD(T)/aug-cc-pVxZ, x = D, T, Q, level of theory.
Many-body decomposition of ΔEatomiz. for the 2Π and 4Σ− states of the XH series (X = C, Si, Ge, Sn) at the RCCSD(T)/aug-cc-pVQZ(-PP)Sn level of theory.
Many-body decomposition of ΔEatomiz. for the 2Π and 4Σ− states of the XH series (X = C, Si, Ge, Sn) at the RCCSD(T)/aug-cc-pVQZ(-PP)Sn level of theory.
Many-body decomposition of the ΔEatomiz. for the X3B1 and a1A1 states of CH2 at the RCCSD(T)/aug-cc-pVxZ, x = D, T, Q, level of theory.
Many-body decomposition of the ΔEatomiz. for the X3B1 and a1A1 states of CH2 at the RCCSD(T)/aug-cc-pVxZ, x = D, T, Q, level of theory.
Many-body decomposition of the ΔEatomiz. for the 3B1 and 1A1 states of the XH2 series (X = C, Si, Ge, Sn) at RCCSD(T)/aug-cc-pVQZ(-PP)Sn level of theory.
Many-body decomposition of the ΔEatomiz. for the 3B1 and 1A1 states of the XH2 series (X = C, Si, Ge, Sn) at RCCSD(T)/aug-cc-pVQZ(-PP)Sn level of theory.
Many-body decomposition of the ΔEatomiz. for the X2A1 state of CH3 at the RCCSD(T)/aug-cc-pVxZ, x = D, T, Q, level of theory.
Many-body decomposition of the ΔEatomiz. for the X2A1 state of CH3 at the RCCSD(T)/aug-cc-pVxZ, x = D, T, Q, level of theory.
Many-body decomposition of the ΔEatomiz. for the X2A1 state of the XH3 series (X = C, Si, Ge, Sn) at the RCCSD(T)/aug-cc-pVQZ(-PP)Sn level of theory.
Many-body decomposition of the ΔEatomiz. for the X2A1 state of the XH3 series (X = C, Si, Ge, Sn) at the RCCSD(T)/aug-cc-pVQZ(-PP)Sn level of theory.
Many-body decomposition of the ΔEatomiz. for the X1A1 state of CH4 at the RCCSD(T)/aug-cc-pVxZ, x = D, T, Q, level of theory.
Many-body decomposition of the ΔEatomiz. for the X1A1 state of CH4 at the RCCSD(T)/aug-cc-pVxZ, x = D, T, Q, level of theory.
Many-body decomposition of the ΔEatomiz. for the X1A1 state of the XH4 series (X = C, Si, Ge, Sn) at the RCCSD(T)/aug-cc-pVQZ(-PP)Sn level of theory.
Many-body decomposition of the ΔEatomiz. for the X1A1 state of the XH4 series (X = C, Si, Ge, Sn) at the RCCSD(T)/aug-cc-pVQZ(-PP)Sn level of theory.
Summary of the MBE for the ΔEatomiz. of the CHn species, n = 1–4, at the RCCSD(T)/aug-cc-pVQZ level of theory.
Summary of the MBE for the ΔEatomiz. of the CHn species, n = 1–4, at the RCCSD(T)/aug-cc-pVQZ level of theory.
Many-body decomposition for the ΔEatomiz. of the SiHn species, n = 1–4, at RCCSD(T)/aug-cc-pVQZ level of theory.
Many-body decomposition for the ΔEatomiz. of the SiHn species, n = 1–4, at RCCSD(T)/aug-cc-pVQZ level of theory.
Many-body decomposition for the ΔEatomiz. of the GeHn species, n = 1–4, at RCCSD(T)/aug-cc-pVQZ level of theory.
Many-body decomposition for the ΔEatomiz. of the GeHn species, n = 1–4, at RCCSD(T)/aug-cc-pVQZ level of theory.
Many-body decomposition for the ΔEatomiz. of the SnHn species, n = 1–4, at RCCSD(T)/aug-cc-pVQZ(-PP)Sn level of theory.
Many-body decomposition for the ΔEatomiz. of the SnHn species, n = 1–4, at RCCSD(T)/aug-cc-pVQZ(-PP)Sn level of theory.
1-B term (eV), 2-B term (eV), atomization energy ΔEatomiz. (eV) with respect to ground state products, and dissociation energy ΔE (eV) with respect to the in situ atomic state without and with BSSE correction (second lines) of the XH molecules, X = C, Si, Ge, and Sn, at the RCCSD(T) level of theory.
Basis set . | Molecule . | 1-B . | 2-B . | ΔEatomiz. . | ΔE . |
---|---|---|---|---|---|
AVDZ | CH (X2Π) | 0.000 | −3.350 | −3.350 | −3.350 |
0.000 | −3.309 | −3.309 | −3.309 | ||
CH (A4Σ−) | 4.000 | −6.707 | −2.707 | −6.707 | |
4.016 | −6.679 | −2.663 | −6.679 | ||
CH (α2Δ) | 1.557 | −1.730 | −0.173 | −1.729 | |
1.570 | −1.713 | −0.143 | −1.713 | ||
AVTZ | CH (X2Π) | 0.000 | −3.571 | −3.571 | −3.571 |
0.000 | −3.548 | −3.548 | −3.548 | ||
CH (A4Σ−) | 4.096 | −6.960 | −2.864 | −6.960 | |
4.111 | −6.950 | −2.839 | −6.950 | ||
CH (α2Δ) | 1.419 | −1.871 | −0.452 | −1.871 | |
1.430 | −1.864 | −0.434 | −1.864 | ||
AVQZ | CH (X2Π) | 0.000 | −3.616 | −3.616 | −3.616 |
0.000 | −3.606 | −3.606 | −3.606 | ||
CH (A4Σ−) | 4.139 | −7.025 | −2.886 | −7.025 | |
4.146 | −7.022 | −2.876 | −7.022 | ||
CH (α2Δ) | 1.391 | −1.895 | −0.504 | −1.895 | |
1.397 | −1.891 | −0.494 | −1.891 | ||
SiH (X2Π) | 0.000 | −3.172 | −3.172 | −3.172 | |
0.000 | −3.165 | −3.165 | −3.165 | ||
SiH (A4Σ−) | 3.907 | −5.404 | −1.497 | −5.404 | |
3.912 | −5.402 | −1.490 | −5.402 | ||
GeH (X2Π) | 0.000 | −2.931 | −2.931 | −2.931 | |
0.000 | −2.925 | −2.925 | −2.925 | ||
GeH (A4Σ−) | 4.394 | −5.505 | −1.111 | −5.506 | |
4.398 | −5.503 | −1.105 | −5.504 | ||
AVQZ(-PP)Sn | SnH (X2Π) | 0.000 | −2.662 | −2.662 | −2.662 |
0.000 | −2.658 | −2.658 | −2.658 | ||
SnH (A4Σ−) | 4.061 | −4.896 | −0.835 | −4.896 | |
4.064 | −4.894 | −0.830 | −4.894 |
Basis set . | Molecule . | 1-B . | 2-B . | ΔEatomiz. . | ΔE . |
---|---|---|---|---|---|
AVDZ | CH (X2Π) | 0.000 | −3.350 | −3.350 | −3.350 |
0.000 | −3.309 | −3.309 | −3.309 | ||
CH (A4Σ−) | 4.000 | −6.707 | −2.707 | −6.707 | |
4.016 | −6.679 | −2.663 | −6.679 | ||
CH (α2Δ) | 1.557 | −1.730 | −0.173 | −1.729 | |
1.570 | −1.713 | −0.143 | −1.713 | ||
AVTZ | CH (X2Π) | 0.000 | −3.571 | −3.571 | −3.571 |
0.000 | −3.548 | −3.548 | −3.548 | ||
CH (A4Σ−) | 4.096 | −6.960 | −2.864 | −6.960 | |
4.111 | −6.950 | −2.839 | −6.950 | ||
CH (α2Δ) | 1.419 | −1.871 | −0.452 | −1.871 | |
1.430 | −1.864 | −0.434 | −1.864 | ||
AVQZ | CH (X2Π) | 0.000 | −3.616 | −3.616 | −3.616 |
0.000 | −3.606 | −3.606 | −3.606 | ||
CH (A4Σ−) | 4.139 | −7.025 | −2.886 | −7.025 | |
4.146 | −7.022 | −2.876 | −7.022 | ||
CH (α2Δ) | 1.391 | −1.895 | −0.504 | −1.895 | |
1.397 | −1.891 | −0.494 | −1.891 | ||
SiH (X2Π) | 0.000 | −3.172 | −3.172 | −3.172 | |
0.000 | −3.165 | −3.165 | −3.165 | ||
SiH (A4Σ−) | 3.907 | −5.404 | −1.497 | −5.404 | |
3.912 | −5.402 | −1.490 | −5.402 | ||
GeH (X2Π) | 0.000 | −2.931 | −2.931 | −2.931 | |
0.000 | −2.925 | −2.925 | −2.925 | ||
GeH (A4Σ−) | 4.394 | −5.505 | −1.111 | −5.506 | |
4.398 | −5.503 | −1.105 | −5.504 | ||
AVQZ(-PP)Sn | SnH (X2Π) | 0.000 | −2.662 | −2.662 | −2.662 |
0.000 | −2.658 | −2.658 | −2.658 | ||
SnH (A4Σ−) | 4.061 | −4.896 | −0.835 | −4.896 | |
4.064 | −4.894 | −0.830 | −4.894 |
1-B term (eV), 2-B term (eV), 3-B term (eV), atomization energy ΔEatomiz. (eV) with respect to ground state products, and dissociation energy ΔE (eV) with respect to the in situ atomic state without and with BSSE correction (second lines) of the XH2 molecules, X = C, Si, Ge, and Sn at the RCCSD(T) level of theory. States are listed in decreasing magnitude of ΔEatomiz.
Basis set . | Molecule . | 1-B . | 2-BXH . | 2-BHH . | 2-B . | 3-B . | ΔEatomiz. . | ΔE . |
---|---|---|---|---|---|---|---|---|
AVDZ | CH2 (X3B1) | 4.000 | −6.705 | 0.259 | −13.151 | 1.404 | −7.747 | −11.747 |
4.031 | −6.696 | 0.249 | −13.142 | 1.449 | −7.661 | −11.692 | ||
CH2 (a1A1) | 0.000 | −3.348 | 0.527 | −6.169 | −1.127 | −7.296 | −7.296 | |
0.000 | −3.317 | 0.516 | −6.117 | −1.098 | −7.214 | −7.214 | ||
AVTZ | CH2 (X3B1) | 4.096 | −6.957 | 0.265 | −13.650 | 1.429 | −8.125 | −12.221 |
4.122 | −6.957 | 0.263 | −13.650 | 1.446 | −8.082 | −12.204 | ||
CH2 (a1A1) | 0.000 | −3.570 | 0.534 | −6.605 | −1.105 | −7.710 | −7.710 | |
0.000 | −3.550 | 0.533 | −6.567 | −1.101 | −7.668 | −7.668 | ||
AVQZ | CH2 (X3B1) | 4.139 | −7.023 | 0.265 | −13.780 | 1.443 | −8.198 | −12.337 |
4.152 | −7.024 | 0.265 | −13.782 | 1.451 | −8.180 | −12.332 | ||
CH2 (a1A1) | 0.000 | −3.614 | 0.534 | −6.694 | −1.102 | −7.795 | −7.795 | |
0.000 | −3.606 | 0.534 | −6.678 | −1.100 | −7.778 | −7.778 | ||
SiH2 (X1A1) | 0.000 | −3.171 | 0.146 | −6.196 | −0.425 | −6.621 | −6.621 | |
0.000 | −3.166 | 0.146 | −6.185 | −0.424 | −6.609 | −6.609 | ||
SiH2 (a3B1) | 3.907 | −5.403 | 0.050 | −10.755 | 1.111 | −5.737 | −9.644 | |
3.916 | −5.403 | 0.050 | −10.756 | 1.116 | −5.725 | −9.640 | ||
GeH2 (X1A1) | 0.000 | −2.930 | 0.109 | −5.752 | −0.359 | −6.111 | −6.111 | |
0.000 | −2.925 | 0.109 | −5.742 | −0.358 | −6.100 | −6.100 | ||
GeH2 (a3B1) | 4.394 | −5.502 | 0.034 | −10.970 | 1.481 | −5.094 | −9.488 | |
4.402 | −5.502 | 0.033 | −10.972 | 1.487 | −5.083 | −9.485 | ||
AVQZ(-PP)Sn | SnH2 (X1A1) | 0.000 | −2.662 | 0.049 | −5.275 | −0.262 | −5.537 | −5.537 |
0.000 | −2.658 | 0.049 | −5.267 | −0.261 | −5.528 | −5.528 | ||
SnH2 (a3B1) | 4.061 | −4.892 | 0.012 | −9.772 | 1.315 | −4.397 | −8.457 | |
4.068 | −4.893 | 0.011 | −9.775 | 1.320 | −4.387 | −8.455 |
Basis set . | Molecule . | 1-B . | 2-BXH . | 2-BHH . | 2-B . | 3-B . | ΔEatomiz. . | ΔE . |
---|---|---|---|---|---|---|---|---|
AVDZ | CH2 (X3B1) | 4.000 | −6.705 | 0.259 | −13.151 | 1.404 | −7.747 | −11.747 |
4.031 | −6.696 | 0.249 | −13.142 | 1.449 | −7.661 | −11.692 | ||
CH2 (a1A1) | 0.000 | −3.348 | 0.527 | −6.169 | −1.127 | −7.296 | −7.296 | |
0.000 | −3.317 | 0.516 | −6.117 | −1.098 | −7.214 | −7.214 | ||
AVTZ | CH2 (X3B1) | 4.096 | −6.957 | 0.265 | −13.650 | 1.429 | −8.125 | −12.221 |
4.122 | −6.957 | 0.263 | −13.650 | 1.446 | −8.082 | −12.204 | ||
CH2 (a1A1) | 0.000 | −3.570 | 0.534 | −6.605 | −1.105 | −7.710 | −7.710 | |
0.000 | −3.550 | 0.533 | −6.567 | −1.101 | −7.668 | −7.668 | ||
AVQZ | CH2 (X3B1) | 4.139 | −7.023 | 0.265 | −13.780 | 1.443 | −8.198 | −12.337 |
4.152 | −7.024 | 0.265 | −13.782 | 1.451 | −8.180 | −12.332 | ||
CH2 (a1A1) | 0.000 | −3.614 | 0.534 | −6.694 | −1.102 | −7.795 | −7.795 | |
0.000 | −3.606 | 0.534 | −6.678 | −1.100 | −7.778 | −7.778 | ||
SiH2 (X1A1) | 0.000 | −3.171 | 0.146 | −6.196 | −0.425 | −6.621 | −6.621 | |
0.000 | −3.166 | 0.146 | −6.185 | −0.424 | −6.609 | −6.609 | ||
SiH2 (a3B1) | 3.907 | −5.403 | 0.050 | −10.755 | 1.111 | −5.737 | −9.644 | |
3.916 | −5.403 | 0.050 | −10.756 | 1.116 | −5.725 | −9.640 | ||
GeH2 (X1A1) | 0.000 | −2.930 | 0.109 | −5.752 | −0.359 | −6.111 | −6.111 | |
0.000 | −2.925 | 0.109 | −5.742 | −0.358 | −6.100 | −6.100 | ||
GeH2 (a3B1) | 4.394 | −5.502 | 0.034 | −10.970 | 1.481 | −5.094 | −9.488 | |
4.402 | −5.502 | 0.033 | −10.972 | 1.487 | −5.083 | −9.485 | ||
AVQZ(-PP)Sn | SnH2 (X1A1) | 0.000 | −2.662 | 0.049 | −5.275 | −0.262 | −5.537 | −5.537 |
0.000 | −2.658 | 0.049 | −5.267 | −0.261 | −5.528 | −5.528 | ||
SnH2 (a3B1) | 4.061 | −4.892 | 0.012 | −9.772 | 1.315 | −4.397 | −8.457 | |
4.068 | −4.893 | 0.011 | −9.775 | 1.320 | −4.387 | −8.455 |
1-B term (eV), 2-B term (eV), 3-B term (eV), 4-B term (eV), atomization energy ΔEatomiz. (eV) with respect to ground state products, and dissociation energy ΔE (eV) with respect to the in situ atomic state without and with BSSE correction (second lines) of the XH3 molecules, X = C, Si, Ge, and Sn at the RCCSD(T) level of theory.
Basis set . | Molecule . | 1-B . | 2-BXH . | 2-BHH . | 2-B . | 3-BXHH . | 3-BHHH . | 3-B . | 4-B . | ΔEatomiz. . | ΔE . |
---|---|---|---|---|---|---|---|---|---|---|---|
AVDZ | CH3 (2A1) | 4.000 | −6.704 | 0.352 | −19.056 | 1.380 | −0.199 | 3.942 | −1.453 | −12.567 | −16.567 |
4.045 | −6.715 | 0.341 | −19.120 | 1.435 | −0.197 | 4.108 | −1.475 | −12.441 | −16.486 | ||
AVTZ | CH3 (2A1) | 4.096 | −6.958 | 0.362 | −19.786 | 1.406 | −0.212 | 4.006 | −1.443 | −13.128 | −17.224 |
4.130 | −6.965 | 0.360 | −19.814 | 1.428 | −0.212 | 4.073 | −1.460 | −13.071 | −17.201 | ||
AVQZ | CH3 (2A1) | 4.139 | −7.023 | 0.363 | −19.980 | 1.420 | −0.213 | 4.048 | −1.451 | −13.244 | −17.383 |
4.156 | −7.027 | 0.362 | −19.995 | 1.430 | −0.213 | 4.078 | −1.459 | −13.220 | −17.376 | ||
SiH3 (2A1) | 3.907 | −5.402 | 0.068 | −16.003 | 1.117 | −0.028 | 3.322 | −1.052 | −9.826 | −13.733 | |
3.918 | −5.405 | 0.068 | −16.013 | 1.124 | −0.028 | 3.343 | −1.058 | −9.809 | −13.727 | ||
GeH3 (2A1) | 4.394 | −5.501 | 0.049 | −16.356 | 1.495 | −0.019 | 4.467 | −1.400 | −8.895 | −13.289 | |
4.405 | −5.505 | 0.049 | −16.367 | 1.503 | −0.019 | 4.490 | −1.407 | −8.879 | −13.284 | ||
AVQZ(-PP)Sn | SnH3 (2A1) | 4.061 | −4.892 | 0.020 | −14.618 | 1.337 | −0.006 | 4.006 | −1.260 | −7.811 | −11.872 |
4.070 | −4.896 | 0.019 | −14.629 | 1.344 | −0.006 | 4.026 | −1.266 | −7.799 | −11.869 |
Basis set . | Molecule . | 1-B . | 2-BXH . | 2-BHH . | 2-B . | 3-BXHH . | 3-BHHH . | 3-B . | 4-B . | ΔEatomiz. . | ΔE . |
---|---|---|---|---|---|---|---|---|---|---|---|
AVDZ | CH3 (2A1) | 4.000 | −6.704 | 0.352 | −19.056 | 1.380 | −0.199 | 3.942 | −1.453 | −12.567 | −16.567 |
4.045 | −6.715 | 0.341 | −19.120 | 1.435 | −0.197 | 4.108 | −1.475 | −12.441 | −16.486 | ||
AVTZ | CH3 (2A1) | 4.096 | −6.958 | 0.362 | −19.786 | 1.406 | −0.212 | 4.006 | −1.443 | −13.128 | −17.224 |
4.130 | −6.965 | 0.360 | −19.814 | 1.428 | −0.212 | 4.073 | −1.460 | −13.071 | −17.201 | ||
AVQZ | CH3 (2A1) | 4.139 | −7.023 | 0.363 | −19.980 | 1.420 | −0.213 | 4.048 | −1.451 | −13.244 | −17.383 |
4.156 | −7.027 | 0.362 | −19.995 | 1.430 | −0.213 | 4.078 | −1.459 | −13.220 | −17.376 | ||
SiH3 (2A1) | 3.907 | −5.402 | 0.068 | −16.003 | 1.117 | −0.028 | 3.322 | −1.052 | −9.826 | −13.733 | |
3.918 | −5.405 | 0.068 | −16.013 | 1.124 | −0.028 | 3.343 | −1.058 | −9.809 | −13.727 | ||
GeH3 (2A1) | 4.394 | −5.501 | 0.049 | −16.356 | 1.495 | −0.019 | 4.467 | −1.400 | −8.895 | −13.289 | |
4.405 | −5.505 | 0.049 | −16.367 | 1.503 | −0.019 | 4.490 | −1.407 | −8.879 | −13.284 | ||
AVQZ(-PP)Sn | SnH3 (2A1) | 4.061 | −4.892 | 0.020 | −14.618 | 1.337 | −0.006 | 4.006 | −1.260 | −7.811 | −11.872 |
4.070 | −4.896 | 0.019 | −14.629 | 1.344 | −0.006 | 4.026 | −1.266 | −7.799 | −11.869 |
1-B term (eV), 2-B term (eV), 3-B term (eV), 4-B term (eV), 5-B term (eV), atomization energy ΔEatomiz. (eV) with respect to ground state products, and dissociation energy ΔE (eV) with respect to the in situ atomic state without and with BSSE correction (second lines) of the XH4 molecules, X = C, Si, Ge, and Sn at the RCCSD(T) level of theory.
Basis set . | Molecule . | 1-B . | 2-BXH . | 2-BHH . | 2-B . | 3-BXHH . | 3-BHHH . | 3-B . | 4-BXHHH . | 4-BHHHH . | 4-B . | 5-B . | ΔEatomiz. . | ΔE . |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
AVDZ | CH4 (1A1) | 4.000 | −6.707 | 0.451 | −24.124 | 1.463 | −0.267 | 7.711 | −1.625 | 0.157 | −6.343 | 1.511 | −17.244 | −21.244 |
4.036 | −6.729 | 0.439 | −24.283 | 1.522 | −0.264 | 8.074 | −1.658 | 0.160 | −6.471 | 1.537 | −17.108 | −21.143 | ||
AVTZ | CH4 (1A1) | 4.096 | −6.960 | 0.461 | −25.070 | 1.488 | −0.282 | 7.804 | −1.615 | 0.171 | −6.290 | 1.500 | −17.961 | −22.057 |
4.131 | −6.976 | 0.460 | −25.147 | 1.515 | −0.281 | 7.963 | −1.634 | 0.171 | −6.363 | 1.519 | −17.897 | −22.028 | ||
AVQZ | CH4 (1A1) | 4.139 | −7.025 | 0.463 | −25.322 | 1.502 | −0.284 | 7.880 | −1.620 | 0.173 | −6.307 | 1.507 | −18.104 | −22.243 |
4.157 | −7.033 | 0.462 | −25.357 | 1.515 | −0.284 | 7.953 | −1.630 | 0.173 | −6.346 | 1.516 | −18.078 | −22.234 | ||
SiH4 (1A1) | 3.907 | −5.402 | 0.074 | −21.164 | 1.124 | −0.032 | 6.620 | −1.083 | 0.013 | −4.318 | 0.961 | −13.994 | −17.901 | |
3.919 | −5.407 | 0.074 | −21.185 | 1.133 | −0.031 | 6.671 | −1.090 | 0.013 | −4.347 | 0.968 | −13.974 | −17.893 | ||
GeH4 (1A1) | 4.394 | −5.500 | 0.054 | −21.675 | 1.503 | −0.021 | 8.933 | −1.432 | 0.008 | −5.721 | 1.311 | −12.758 | −17.152 | |
4.406 | −5.506 | 0.054 | −21.699 | 1.512 | −0.021 | 8.989 | −1.441 | 0.008 | −5.755 | 1.319 | −12.740 | −17.146 | ||
AVQZ(-PP)Sn | SnH4 (1A1) | 4.061 | −4.890 | 0.021 | −19.434 | 1.334 | −0.007 | 7.979 | −1.260 | 0.002 | −5.039 | 1.177 | −11.255 | −15.316 |
4.071 | −4.895 | 0.021 | −19.456 | 1.343 | −0.007 | 8.029 | −1.268 | 0.002 | −5.069 | 1.185 | −11.240 | −15.312 |
Basis set . | Molecule . | 1-B . | 2-BXH . | 2-BHH . | 2-B . | 3-BXHH . | 3-BHHH . | 3-B . | 4-BXHHH . | 4-BHHHH . | 4-B . | 5-B . | ΔEatomiz. . | ΔE . |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
AVDZ | CH4 (1A1) | 4.000 | −6.707 | 0.451 | −24.124 | 1.463 | −0.267 | 7.711 | −1.625 | 0.157 | −6.343 | 1.511 | −17.244 | −21.244 |
4.036 | −6.729 | 0.439 | −24.283 | 1.522 | −0.264 | 8.074 | −1.658 | 0.160 | −6.471 | 1.537 | −17.108 | −21.143 | ||
AVTZ | CH4 (1A1) | 4.096 | −6.960 | 0.461 | −25.070 | 1.488 | −0.282 | 7.804 | −1.615 | 0.171 | −6.290 | 1.500 | −17.961 | −22.057 |
4.131 | −6.976 | 0.460 | −25.147 | 1.515 | −0.281 | 7.963 | −1.634 | 0.171 | −6.363 | 1.519 | −17.897 | −22.028 | ||
AVQZ | CH4 (1A1) | 4.139 | −7.025 | 0.463 | −25.322 | 1.502 | −0.284 | 7.880 | −1.620 | 0.173 | −6.307 | 1.507 | −18.104 | −22.243 |
4.157 | −7.033 | 0.462 | −25.357 | 1.515 | −0.284 | 7.953 | −1.630 | 0.173 | −6.346 | 1.516 | −18.078 | −22.234 | ||
SiH4 (1A1) | 3.907 | −5.402 | 0.074 | −21.164 | 1.124 | −0.032 | 6.620 | −1.083 | 0.013 | −4.318 | 0.961 | −13.994 | −17.901 | |
3.919 | −5.407 | 0.074 | −21.185 | 1.133 | −0.031 | 6.671 | −1.090 | 0.013 | −4.347 | 0.968 | −13.974 | −17.893 | ||
GeH4 (1A1) | 4.394 | −5.500 | 0.054 | −21.675 | 1.503 | −0.021 | 8.933 | −1.432 | 0.008 | −5.721 | 1.311 | −12.758 | −17.152 | |
4.406 | −5.506 | 0.054 | −21.699 | 1.512 | −0.021 | 8.989 | −1.441 | 0.008 | −5.755 | 1.319 | −12.740 | −17.146 | ||
AVQZ(-PP)Sn | SnH4 (1A1) | 4.061 | −4.890 | 0.021 | −19.434 | 1.334 | −0.007 | 7.979 | −1.260 | 0.002 | −5.039 | 1.177 | −11.255 | −15.316 |
4.071 | −4.895 | 0.021 | −19.456 | 1.343 | −0.007 | 8.029 | −1.268 | 0.002 | −5.069 | 1.185 | −11.240 | −15.312 |
Bond distances RXH (Å) and angles φHΧH (degrees) for the various states of XHn, (X = C, Si, Ge, Sn; n = 1–4) at the RCCSD(T) level of theory.
. | . | CHn . | SiHn . | GeHn . | SnHn . | ||
---|---|---|---|---|---|---|---|
. | . | AVDZ . | AVTZ . | AVQZ . | AVQZ . | AVQZ . | AVQZ . |
XH(Χ2Π) | RXH | 1.1400 | 1.1219 | 1.1203 | 1.5242 | 1.6028 | 1.7901 |
XH(A4Σ−) | RXH | 1.1066 | 1.0908 | 1.0894 | 1.4969 | 1.5694 | 1.7550 |
XH(α2Δ) | RXH | 1.1229 | 1.1069 | 1.1056 | |||
XH2(3B1) | RXH | 1.0943 | 1.0791 | 1.0775 | 1.4815 | 1.5449 | 1.7281 |
φHΧH | 66.53 | 66.78 | 66.81 | 59.19 | 59.70 | 59.31 | |
XH2(1A1) | RXH | 1.1271 | 1.1107 | 1.1088 | 1.5184 | 1.5963 | 1.7841 |
φHΧH | 50.57 | 50.94 | 51.00 | 46.14 | 45.82 | 45.60 | |
XH3(X2A1) | RXH | 1.0932 | 1.0795 | 1.0780 | 1.4810 | 1.5443 | 1.7289 |
φHΧH | 120.00 | 120.00 | 120.00 | 107.59 | 107.68 | 109.21 | |
XH4(X1A1) | RXH | 1.1027 | 1.0899 | 1.0883 | 1.4803 | 1.5414 | 1.7289 |
φHΧH | 109.47 | 109.47 | 109.47 | 109.49 | 109.47 | 109.21 |
. | . | CHn . | SiHn . | GeHn . | SnHn . | ||
---|---|---|---|---|---|---|---|
. | . | AVDZ . | AVTZ . | AVQZ . | AVQZ . | AVQZ . | AVQZ . |
XH(Χ2Π) | RXH | 1.1400 | 1.1219 | 1.1203 | 1.5242 | 1.6028 | 1.7901 |
XH(A4Σ−) | RXH | 1.1066 | 1.0908 | 1.0894 | 1.4969 | 1.5694 | 1.7550 |
XH(α2Δ) | RXH | 1.1229 | 1.1069 | 1.1056 | |||
XH2(3B1) | RXH | 1.0943 | 1.0791 | 1.0775 | 1.4815 | 1.5449 | 1.7281 |
φHΧH | 66.53 | 66.78 | 66.81 | 59.19 | 59.70 | 59.31 | |
XH2(1A1) | RXH | 1.1271 | 1.1107 | 1.1088 | 1.5184 | 1.5963 | 1.7841 |
φHΧH | 50.57 | 50.94 | 51.00 | 46.14 | 45.82 | 45.60 | |
XH3(X2A1) | RXH | 1.0932 | 1.0795 | 1.0780 | 1.4810 | 1.5443 | 1.7289 |
φHΧH | 120.00 | 120.00 | 120.00 | 107.59 | 107.68 | 109.21 | |
XH4(X1A1) | RXH | 1.1027 | 1.0899 | 1.0883 | 1.4803 | 1.5414 | 1.7289 |
φHΧH | 109.47 | 109.47 | 109.47 | 109.49 | 109.47 | 109.21 |
XH (X = C, Si, Ge, Sn): The analysis for the ground (2Π), first (4Σ−), and second (2Δ) excited states of CH is shown in Fig. 2. Energy differences are taken with respect to the ground state of the two atoms, viz., C(3P) + H(2S). The 2Π ground state of CH correlates with the corresponding ground state atomic states, i.e., the in situ atomic state of C in the ground state of CH is the atomic ground 3P state. In other words, the 1-B term is zero since there is no need to promote the ground 3P state of the C atom to form the C–H bond in its ground 2Π state. In this case, the 2-B term is identical with the atomization energy ΔEatomiz⋅ However, the situation is different for the first and second excited states of the CH molecule. The in situ electronic state of the C atom in the first 4Σ− excited state of CH is the atomic 5S state, so the (positive) 1-B term is the energy required to promote the C atom from 3P → 5S. Accordingly, the 2-B term is the energy difference between the C(5S) + H(2S) and CH(4Σ−) energy levels, which is also the difference between the total atomization energy (ΔEatomiz⋅) and the 1-B term. Similarly, the in situ electronic state of the C atom in the second 2Δ state if CH is the atomic 2D state and the 1-B and 2-B terms are computed accordingly. The results with the various basis sets (AVDZ, AVTZ, and AVQZ) are denoted with different colors for the different energy levels obtained with the three basis sets in Fig. 2. The individual 2-B terms for the ground (2Π), first (4Σ−), and second (2Δ) excited states of CH are decreasing in that order (cf. Table I), and the presence of the repulsive 1-B term for the last two determines the overall order in the atomization energies with respect to the atomic ground states, as shown in Fig. 2. The σ bond length of the 4Σ− state is shorter than the corresponding value of the X2Π state by 0.03 Å, showing that the bonding of the 4Σ− state is stronger than in the X2Π state. The 2-B term of the 4Σ− state is significantly larger (double) than the 2-B term of X2Π. This happens because the formation of a σ bond with a highly open shell system, such as C(5S), significantly stabilizes the carbon atom and consequently the whole C–H system. On the contrary, the C(3P) is lower in energy than C(5S), it has only two unpaired electrons, and, thus, even though the σ bond stabilize the C–H molecule, this stabilization is not dramatically large.
The situation for the ground (2Π) and the first (4Σ−) excited states of SiH, GeH, and SnH is similar to that for CH; the results for the XH series (X = C, Si, Ge, Sn) are graphically summarized in Fig. 3, and the individual numbers (including the ones corrected for BSSE) are listed in Table I. The decrease of the individual 2-B terms for the respective ground (2Π) and excited (A4Σ−) states in the XH series monotonically follows the trends of increasing X–H separations (cf. Table V) in an almost linear fashion.
XH2 (X = C, Si, Ge, Sn): The MBE analysis for the ground (X3B1) and the first excited (a1A1) states of CH2 is schematically shown in Fig. 4, where the zero in the energy scale is taken with respect to the C(3P) + 2 × H(2S) asymptote. The ground (X3B1) state of CH2 correlates with the C(5S) + H(2S) + H(2S) atomic states so the 1-B term is positive and corresponds to the 3P → 5S promotion energy. The 2-B term is negative, whereas there is a smaller positive 3-B term. The MBE based on the various fragments allows for the further attribution of the individual terms to specific interactions between the constituent atoms. As can be seen from Table II, the main contribution to the total 2-B term (being the sum of the individual interactions between C–H and H–H) comes from the attractive (stabilizing) 2-BCH term with the remaining 2-BHH term being quite small and repulsive (destabilizing), amounting to just ∼4% of the total 2-B interaction. In contrast, for the first (a1A1) excited state of CH2, also shown in Fig. 4, the 1-B term is zero (since the in situ electronic state of C in the (a1A1) state of CH2 is the atomic 3P state), and, in this case, both the 2- and 3-B terms are negative. This is expected for the 3-B term for the 1A1 state of CH2 and for the rest of the XH2 molecules (see below) because this state corresponds to a closed shell system, and, thus, the simultaneous existence of the three atoms further stabilize it. On the contrary, this not the case for the X3B1 state in which the system is not closed shell and, thus, it follows the usual trend, i.e., the many-body terms oscillate between the positive and negative values.
The analysis for the combined results for the XH2 series, X = C, Si, Ge, Sn, are schematically shown in Fig. 5 and listed in Table II. A notable difference between CH2 and the rest of the XH2 series (X = Si, Ge, Sn) is that the order of the ground/first excited state is reversed. Indeed, as can be seen from Figs. 4 and 5 and the results of Table I, for CH2, the ground state is the 3B1 and the first excited the 1A1 state, whereas, for X = Si, Ge, Sn, the ground state of XH2 is the 1A1 and the first excited the 3B1 state. Therefore, the in situ electronic state of the carbon atom in the ground 3B1 state of CH2 is C(5S), whereas the in situ electronic state of the Si/Ge/Sn in the ground state of SiH2/GeH2/SnH2 is Si/Ge/Sn (3P) (see Figs. 4 and 5). The difference on the type of the ground state results from the fact that the Si, Ge, and Sn atoms are larger than C, forming significant larger X–H bond lengths and this favors the formation of two X–H bonds from the X(3P) rather than from the X(5S) states for X = Si, Ge, Sn. Note that the bond arising from the atomic 5S state is stabilized via shorter X–H bond lengths than the one arising from the X(3P) atomic state. Additionally, the 2-BXH and 2-BHH terms are decreasing in the series for both the ground and the excited states, in line with the corresponding monotonic increase of the X–H bond distance (cf. Table V). Note that the 3-B term for the ground (X3B1) state is positive (destabilizing), whereas the one for the first excited (a1A1) state is negative (stabilizing) in the series. For both states, the 3-B is much smaller than the 2-B term, as seen from Fig. 5 and Table II.
In the following, we elaborate on an important detail of the MBE analysis related to the electronic states used to compute the energies of the fragments. As it can be seen from Figs. 2 and 3, the 2Π ground state of XH (X = C, Si, Ge, Sn) is formed from the respective X(3P) + H(2S) states, whereas the first excited (4Σ−) state from the X(5S) + H(2S) states. The ground 3B1 state of CH2 is formed (cf. Fig. 4) from the C(5S) + 2H(2S) states and, when evaluating the MBE for that state, the two-body “CH” term is computed with CH at its excited 4Σ− state [also formed from C(5S) + H(2S)]. In contrast, the first excited a1A1 state of CH2 is formed (cf. Fig. 4) from C(3P) + 2H(2S) and the two-body “CH” term for that state is computed with CH at its ground 2Π state [also formed from C(3P) + H(2S)]. The calculation of the two-body “XH” term in XH2 for X = Si, Ge, Sn is evaluated in a similar manner while also noting that for these molecules the order of the ground and first excited states flip with respect to CH2 (see Fig. 5 and Table II). This protocol is also followed in the evaluation of the MBE for the larger molecules.
XH3 (X = C, Si, Ge, Sn): The MBE for the ground (X2A1) state of CH3 is schematically shown in Fig. 6. The ground state of CH3 correlates with the C(5S) + H(2S) + H(2S) + H(2S) atomic states, viz., there is a positive 1-B term corresponding to the promotion 3P → 5S for the carbon atom. The 3-B term is smaller than the 2-B and positive, whereas the 4-B is even smaller than the 3-B and negative. The trends for the MBE of the XH3 series, X = C, Si, Ge, Sn, schematically shown in Fig. 7 and listed in Table III, are similar to the ones for CH3 with the terms oscillating between the positive (destabilizing) and negative (stabilizing) values, whereas they overall decrease in magnitude with rank k after the 2-B term, as can also be seen from Table III. The MBE, therefore, seems to be “converging” albeit in a slow, oscillating manner. Again, the total 2-BXH (sum of three identical components) is the major contributor to the 2-B term with the 2-BHH term being quite small and repulsive as in the XH2 series; they both decrease in magnitude in the series. With regard to the 3-B term, the signs of the individual components are reversed when compared to the 2-B term: the 3-BXHH is positive, whereas the 3-BHHH is very small and negative.
XH4 (X = C, Si, Ge, Sn): The in situ atomic state of carbon in the ground (X1A1) state of CH4 is 5S, giving rise to a positive 1-B energy. The negative (stabilizing) 2-B term is the largest one among the higher order terms, which are oscillating between the positive and negative values and are decreasing in size after the 2-B term as can be seen from Fig. 8. The same trends are observed for the rest of the XH4 series (X = C, Si, Ge, Sn) as shown in Fig. 9 and Table IV. The 3-BXHH and 3-BHHH terms are similar in sign, magnitude, and trend across the XH4 series as in the XH3 series. The same behavior is seen for the 4-BXHHH and 4-BHHHH terms (cf. Table IV). A notable difference is that the total (positive) 3-B term almost cancels the total (negative) 4-B term. The 5-B term is small (∼10% of the atomization energy).
Trends in the MBE of XHn (X = C, Si, Ge, Sn): The MBE for the XHn series is summarized in Figs. 10–13 for X = C, Si, Ge, and Sn, respectively. The trends in both the sign and magnitude of the individual MBE terms are similar across the series, namely, that the 1-B term is zero for n = 1 and positive (energy for the 3P → 5S promotion of the carbon atom) for n = 2–4 with the 2-B term being the largest one in the MBE and the rest of the terms oscillating in sign and diminishing after that. The behavior of the MBE is similar across the series. The correlation between the X–H distances and the magnitude of the individual 2-BXH terms, discussed earlier, is shown in Fig. 14 for the XHn series. The linear correlation across the XHn series for each n confirms that the X–H distance is a descriptor of the magnitude of the individual 2-BXH terms. Note the difference in the magnitude of the 2-B terms for the XH series due to the absence of a 1-B term for this case. This is because the individual 2-B terms are determined with respect to the C(3P) + H(2S) for XH and with respect to the C(5S) + n × H(2S) for the XHn, n = 2, 3, 4 series. It is interesting that this descriptor is independent of n, i.e., the size of the XHn molecules. The linear fits corresponding to the same in situ atoms are almost identical as shown in Fig. 14
Correlation between the individual 2-BXH term and the X–H distance for the XHn series, X = C, Si, Ge, Se and n = 1–4. Note the different magnitude for the XH species due to the fact that the energy difference is taken with respect to the ground state atoms (consistent with the absence of the 1-B term) for that case.
Correlation between the individual 2-BXH term and the X–H distance for the XHn series, X = C, Si, Ge, Se and n = 1–4. Note the different magnitude for the XH species due to the fact that the energy difference is taken with respect to the ground state atoms (consistent with the absence of the 1-B term) for that case.
The variation of the individual 2-BHH and 2-BXH terms for the XHn series, X = C, Si, Ge, Se and n = 2–4 is shown in Fig. 15. In the left panel, which shows the variation of the 2-BHH across the series, the filled symbols trace states in which X is at the in situ 5S atomic state, whereas the open symbols denote states in which X is at the in situ 3P atomic state. The larger relative increase in the 2-BHH term across the CHn series is due to the fact that the hydrogen atoms are closer to one another with increasing n as the result of the shorter C–H distances being in the 1.08–1.12 Å range (cf. Table V). In contrast, the 2-BHH terms for XHn, where X = Si, Ge, and Sn, are almost the same for n = 2–4, a result of the longer X–H distances (1.50–1.80 Å range, cf. Table V) that bring the hydrogen atoms further apart. The variation of the 2-BXH term across the series is shown on the right panel of Fig. 15, where the two different curves refer to the calculation when the heavy atom is at the in situ 5S and 3P atomic states in the molecule. As a general trend, when X is at the atomic 3P state in the molecule, we observe a monotonic decrease of the 2-BXH term with the size of the X atom. This is consistent with the fact that the X–H bond distance, already being identified as a descriptor of the 2-BXH term (cf. Fig. 14), increases across the series. When X is at the in situ atomic 5S state, the 2-BXH is also decreasing across the series, except for Ge. This “anomaly” is attributed to the fact that the 3P → 5S energy is the largest one for Ge (cf. Tables I–IV). It is 6.1% larger than C, 12.5% larger than Si, and 8.2% larger than Sn, resulting in the 2-BGe-H term of Ge(5S) to be further stabilized.
Variation of the individual 2-BHH and 2-BXH terms for the XHn series, X = C, Si, Ge, Se and n = 2–4 at the RCCSD(T)/AVQZ(-PP)Sn level of theory. In the left panel, solid/open symbols denote the states in which X is at the 5S/3P atomic states.
Variation of the individual 2-BHH and 2-BXH terms for the XHn series, X = C, Si, Ge, Se and n = 2–4 at the RCCSD(T)/AVQZ(-PP)Sn level of theory. In the left panel, solid/open symbols denote the states in which X is at the 5S/3P atomic states.
B. Incremental bond energies: is there a “first row anomaly?”
The incremental Hn−1X–H bond energies for X = C, Si, Ge, Sn are shown in Fig. 16. In the left panel of that figure, the energies are computed with respect to the lowest in energy (ground states) of the Hn−1X molecule. Following our previous discussion in Sec. III A, these are 3B1 for CH2 and 1A1 for SiH2, GeH2, and SnH2 (indicated on the left panel of Fig. 16 for n = 2). The left panel of Fig. 16 is the same as the right panel of Fig. 9 of Ref. 76, but extended for X = Sn. As discussed in this earlier publication and reproduced by our results, the trend in the incremental bond energies with respect to the lowest in energy states is qualitatively different between the CHn and the rest of XHn series: indeed, there exists a “peak” for CH3 (the bond energy for CH3 is larger than the ones for CH2 and CH5), whereas there is a “dip” for the XHn, X = Si, Ge, Sn, series (the bond energy for XH3 is lower than that for XH2 and XH5 when X = Si, Ge, Sn).
The incremental Hn−1X–H bond energy, X = C, Si, Ge, Sn. Left panel: energies with respect to the lowest in energy of the Hn−1X molecule. Right panel: energies with respect to the Hn−1X molecule, where X is at the 5S state (solid line) and at the 3P state (dotted line). All energies are computed at the RCCSD(T)/AVQZ(-PP)Sn level of theory.
The incremental Hn−1X–H bond energy, X = C, Si, Ge, Sn. Left panel: energies with respect to the lowest in energy of the Hn−1X molecule. Right panel: energies with respect to the Hn−1X molecule, where X is at the 5S state (solid line) and at the 3P state (dotted line). All energies are computed at the RCCSD(T)/AVQZ(-PP)Sn level of theory.
However, when the bond energies are computed with respect to the molecular states having the same in situ atomic state (i.e., not necessarily the lowest energy ones but the ones correlating with the same atomic states), the situation is different as shown in the right panel of Fig. 16. In that panel, the various states, with respect to which the individual incremental energies were computed, are noted. The Hn−1X–H incremental bond energies are obtained with respect to the Hn−1X molecule, where X is at either the 5S (solid line) or at the 3P (dotted line) atomic states. When this protocol is followed, the variation of the bond energies with n is qualitatively similar across the series and the concept of the “first row anomaly” is not justified. One can nevertheless argue that the (first row) carbon atom can be still considered different than the (second and subsequent rows) Si, Ge, and Sn atoms in lieu of the “flipping” of the ground/excited states for n = 2 in the series (CH2 vs SiH2/GeH2/SnH2). However, this qualitative change is not a property of the individual atoms per se but rather their different behavior in just the XH2, but not the rest of the hydrides.
IV. CONCLUSIONS
We have described a novel decomposition scheme for the MBE in molecules and applied it to the XHn series (X = C, Si, Ge, Sn; n = 1–4). The protocol allows for the decomposition of the atomization energy in terms of atoms, dimers, trimers, etc. In the present implementation of the MBE that is based on the breaking of covalent bonds to define subsystems, the 1-B term is both qualitative and quantitatively different than the analogous 1-B term that has been popularized in the MBE of aqueous ionic systems. When breaking hydrogen bonds to define the various subsystems, the 1-B term represents the geometrical distortion94 of the individual fragments from their gas phase geometries due to the interaction with other neighboring molecules or ions. It amounts to a few kcal/mol and it can be indirectly probed experimentally by infrared (IR) spectroscopy,99,100 which records the change in the position of the individual vibrational bands from the gas phase as a result of the change in the fragment’s geometry from the isolated species. In contrast, when breaking covalent bonds, the 1-B represents the electronic excitation of an individual atom101 to bring it to its in situ electronic state in the molecule, and it amounts to a few eV (i.e., it is about two orders of magnitude larger) and can be probed by Ultraviolet–Visible (UV) spectroscopy.
We have found that the MBE in the XHn series is oscillating between positive and negative values, and it is converging with increasing rank of the expansion. Among the individual terms, the 2-B is by far the largest one in the MBE. The X–H distance is a good descriptor of the strength of the 2-BXH term, and its variation across the series can be attributed to the respective geometrical changes. The analysis can offer an alternative explanation for the purported “first row anomaly” that is based upon the different variation of the incremental bond energies for CHn compared to XHn, X = Si, Ge, Sn, when these bond energies are evaluated with respect to the lowest energies (ground states) of the members in the series. However, there is a “flipping” between the ground and the first excited state in CH2 (ground is the 3B1 and excited is the 1A1 states) compared to XH2, where X = Si, Ge, and Sn (ground is the 1A1 and excited is the 3B1 state). When these incremental binding energies are evaluated with respect to the molecular states that have the same in situ atomic state, their variation is the same with n for all X (C, Si, Ge, Sn) in the XHn series and the concept of the “first row anomaly” is, thus, not justified.
Note that the present analysis is simplified due to the presence of just one heavy atom (C, Si, Ge, Sn) in each of the systems studied and can be much more complex when more than one heavy atom is involved. Nevertheless, it provides a straightforward extension of the popular MBE for hydrogen bonded systems to incorporate the breaking of covalent bonds and offers valuable insights into the chemical bonding of chemical systems.
ACKNOWLEDGMENTS
S.S.X. was supported from the Center for Scalable Predictive methods for Excitations and Correlated phenomena (SPEC), which is funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division as part of the Computational Chemical Sciences (CCS) program at Pacific Northwest National Laboratory. Battelle operates the Pacific Northwest National Laboratory for the U.S. Department of Energy. This research used computer resources provided by the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
AUTHOR DECLARATIONS
Conflict of Interest
The authors have no conflicts to disclose.
DATA AVAILABILITY
The data that support the findings of this study are available from the corresponding author upon reasonable request.