We report vibrational spectra of the H2-tagged, cryogenically cooled X− · HOCl (X = Cl, Br, and I) ion–molecule complexes and analyze the resulting band patterns with electronic structure calculations and an anharmonic theoretical treatment of nuclear motions on extended potential energy surfaces. The complexes are formed by “ligand exchange” reactions of X− · (H2O)n clusters with HOCl molecules at low pressure (∼10−2 mbar) in a radio frequency ion guide. The spectra generally feature many bands in addition to the fundamentals expected at the double harmonic level. These “extra bands” appear in patterns that are similar to those displayed by the X− · HOD analogs, where they are assigned to excitations of nominally IR forbidden overtones and combination bands. The interactions driving these features include mechanical and electronic anharmonicities. Particularly intense bands are observed for the v = 0 → 2 transitions of the out-of-plane bending soft modes of the HOCl molecule relative to the ions. These involve displacements that act to break the strong H-bond to the ion, which give rise to large quadratic dependences of the electric dipoles (electronic anharmonicities) that drive the transition moments for the overtone bands. On the other hand, overtone bands arising from the intramolecular OH bending modes of HOCl are traced to mechanical anharmonic coupling with the v = 1 level of the OH stretch (Fermi resonances). These interactions are similar in strength to those reported earlier for the X− · HOD complexes.
Skip Nav Destination
CHORUS
Article navigation
7 May 2022
Research Article|
May 05 2022
Electronic and mechanical anharmonicities in the vibrational spectra of the H-bonded, cryogenically cooled X− · HOCl (X=Cl, Br, I) complexes: Characterization of the strong anionic H-bond to an acidic OH group
Santino J. Stropoli
;
Santino J. Stropoli
1
Sterling Chemistry Laboratory, Department of Chemistry, Yale University
, New Haven, Connecticut 06520, USA
Search for other works by this author on:
Thien Khuu
;
Thien Khuu
1
Sterling Chemistry Laboratory, Department of Chemistry, Yale University
, New Haven, Connecticut 06520, USA
Search for other works by this author on:
Mark A. Boyer
;
Mark A. Boyer
2
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
Search for other works by this author on:
Natalia V. Karimova
;
Natalia V. Karimova
3
Department of Chemistry, University of California Irvine
, Irvine, California 92697, USA
Search for other works by this author on:
Coire F. Gavin-Hanner
;
Coire F. Gavin-Hanner
2
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
Search for other works by this author on:
Sayoni Mitra
;
Sayoni Mitra
1
Sterling Chemistry Laboratory, Department of Chemistry, Yale University
, New Haven, Connecticut 06520, USA
Search for other works by this author on:
Anton L. Lachowicz
;
Anton L. Lachowicz
1
Sterling Chemistry Laboratory, Department of Chemistry, Yale University
, New Haven, Connecticut 06520, USA
Search for other works by this author on:
Nan Yang
;
Nan Yang
1
Sterling Chemistry Laboratory, Department of Chemistry, Yale University
, New Haven, Connecticut 06520, USA
Search for other works by this author on:
R. Benny Gerber
;
R. Benny Gerber
a)
3
Department of Chemistry, University of California Irvine
, Irvine, California 92697, USA
4
Institute of Chemistry and The Fritz Haber Research Center, The Hebrew University
, Jerusalem 91904, Israel
a)Authors to whom correspondence should be addressed: [email protected]; [email protected]; and [email protected]
Search for other works by this author on:
Anne B. McCoy
;
Anne B. McCoy
a)
2
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
a)Authors to whom correspondence should be addressed: [email protected]; [email protected]; and [email protected]
Search for other works by this author on:
Mark A. Johnson
Mark A. Johnson
a)
1
Sterling Chemistry Laboratory, Department of Chemistry, Yale University
, New Haven, Connecticut 06520, USA
a)Authors to whom correspondence should be addressed: [email protected]; [email protected]; and [email protected]
Search for other works by this author on:
a)Authors to whom correspondence should be addressed: [email protected]; [email protected]; and [email protected]
J. Chem. Phys. 156, 174303 (2022)
Article history
Received:
December 21 2021
Accepted:
April 05 2022
Citation
Santino J. Stropoli, Thien Khuu, Mark A. Boyer, Natalia V. Karimova, Coire F. Gavin-Hanner, Sayoni Mitra, Anton L. Lachowicz, Nan Yang, R. Benny Gerber, Anne B. McCoy, Mark A. Johnson; Electronic and mechanical anharmonicities in the vibrational spectra of the H-bonded, cryogenically cooled X− · HOCl (X=Cl, Br, I) complexes: Characterization of the strong anionic H-bond to an acidic OH group. J. Chem. Phys. 7 May 2022; 156 (17): 174303. https://doi.org/10.1063/5.0083078
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Dielectric profile at the Pt(111)/water interface
Jia-Xin Zhu, Jun Cheng, et al.
Related Content
The vibrational dynamics of 3D HOCl above dissociation
J. Chem. Phys. (March 2015)
Quasi-classical simulations of resonance Raman spectra based on path integral linearization
J. Chem. Phys. (July 2023)
Infrared spectroscopy of HOCl embedded in superfluid helium nanodroplets: Probing the dynamical response of the solvent
J. Chem. Phys. (July 2012)