We show that the energy of a perturbed system can be fully recovered from the unperturbed system’s electron density. We derive an alchemical integral transform by parametrizing space in terms of transmutations, the chain rule, and integration by parts. Within the radius of convergence, the zeroth order yields the energy expansion at all orders, restricting the textbook statement by Wigner that the p-th order wave function derivative is necessary to describe the (2p + 1)-th energy derivative. Without the need for derivatives of the electron density, this allows us to cover entire chemical neighborhoods from just one quantum calculation instead of single systems one by one. Numerical evidence presented indicates that predictive accuracy is achieved in the range of mHa for the harmonic oscillator or the Morse potential and in the range of machine accuracy for hydrogen-like atoms. Considering isoelectronic nuclear charge variations by one proton in all multi-electron atoms from He to Ne, alchemical integral transform based estimates of the relative energy deviate by only few mHa from corresponding Hartree–Fock reference numbers.
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28 October 2022
Research Article|
October 26 2022
Relative energies without electronic perturbations via alchemical integral transform Available to Purchase
Simon León Krug
;
Simon León Krug
(Conceptualization, Data curation, Formal analysis, Methodology, Software, Visualization, Writing – original draft, Writing – review & editing)
1
University of Vienna, Computational Materials Physics
, Kolingasse 14-16, 1090 Vienna, Austria
2
Machine Learning Group, Technische Universität Berlin and Institute for the Foundations of Learning and Data
, 10587 Berlin, Germany
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Guido Falk von Rudorff
;
Guido Falk von Rudorff
(Conceptualization, Formal analysis, Investigation, Methodology, Supervision, Visualization, Writing – original draft)
1
University of Vienna, Computational Materials Physics
, Kolingasse 14-16, 1090 Vienna, Austria
3
Institute for Pure and Applied Mathematics (IPAM), University of California, Los Angeles
, 460 Portola Plaza, Los Angeles, California 90095, USA
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O. Anatole von Lilienfeld
O. Anatole von Lilienfeld
a)
(Conceptualization, Formal analysis, Investigation, Methodology, Project administration, Resources, Supervision, Visualization, Writing – review & editing)
2
Machine Learning Group, Technische Universität Berlin and Institute for the Foundations of Learning and Data
, 10587 Berlin, Germany
4
Vector Institute for Artificial Intelligence
, Toronto, Ontario, M5S 1M1, Canada
5
Departments of Chemistry, Materials Science and Engineering, and Physics, University of Toronto
, St. George Campus, Toronto, Ontario M5S 1A7, Canada
a)Author to whom correspondence should be addressed: [email protected]
Search for other works by this author on:
Simon León Krug
1,2
Guido Falk von Rudorff
1,3
O. Anatole von Lilienfeld
2,4,5,a)
1
University of Vienna, Computational Materials Physics
, Kolingasse 14-16, 1090 Vienna, Austria
2
Machine Learning Group, Technische Universität Berlin and Institute for the Foundations of Learning and Data
, 10587 Berlin, Germany
3
Institute for Pure and Applied Mathematics (IPAM), University of California, Los Angeles
, 460 Portola Plaza, Los Angeles, California 90095, USA
4
Vector Institute for Artificial Intelligence
, Toronto, Ontario, M5S 1M1, Canada
5
Departments of Chemistry, Materials Science and Engineering, and Physics, University of Toronto
, St. George Campus, Toronto, Ontario M5S 1A7, Canada
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 157, 164109 (2022)
Article history
Received:
July 19 2022
Accepted:
September 29 2022
Citation
Simon León Krug, Guido Falk von Rudorff, O. Anatole von Lilienfeld; Relative energies without electronic perturbations via alchemical integral transform. J. Chem. Phys. 28 October 2022; 157 (16): 164109. https://doi.org/10.1063/5.0111511
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