Time-Dependent Linear-Response Variational Monte Carlo
In: Advances in Quantum Chemistry Advances in Quantum Chemistry, Elsevier, 2017, Novel Electronic Structure Theory: General Innovations and Strongly Correlated Systems Advances in Quantum Chemistry, 2017, Novel Electronic Structure Theory: General Innovations and Strongly Correlated Systems; (2017)
Online
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Zugriff:
We present the extension of variational Monte Carlo (VMC) to the calculation of electronic excitation energies and oscillator strengths using time-dependent linear-response theory. By exploiting the analogy existing between the linear method for wave-function optimisation and the generalised eigenvalue equation of linear-response theory, we formulate the equations of linear-response VMC (LR-VMC). This LR-VMC approach involves the first-and second-order derivatives of the wave function with respect to the parameters. We perform first tests of the LR-VMC method within the Tamm-Dancoff approximation using single-determinant Jastrow-Slater wave functions with different Slater basis sets on some singlet and triplet excitations of the beryllium atom. Comparison with reference experimental data and with configuration-interaction-singles (CIS) results shows that LR-VMC generally outperforms CIS for excitation energies and is thus a promising approach for calculating electronic excited-state properties of atoms and molecules.
Advances in Quantum Chemistry, 2017, Novel Electronic Structure Theory: General Innovations and Strongly Correlated Systems
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Time-Dependent Linear-Response Variational Monte Carlo
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| Autor/in / Beteiligte Person: | Mussard, Bastien ; Coccia, Emanuele ; Assaraf, Roland ; Otten, Matt ; Umrigar, C. J. ; Toulouse, Julien ; Mussard, B ; Coccia, E ; Assaraf, R ; Otten, M ; Umrigar, C J ; Toulouse, J. ; Laboratoire de chimie théorique (LCT) ; Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) ; Institut des Sciences du Calcul et des Données (ISCD) ; Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU) ; Dipartimento di Scienze Fisiche e Chimiche [L'Aquila] ; Università degli Studi dell'Aquila (UNIVAQ) ; Laboratory of Atomic and Solid State Physics [Ithaca] (LASSP) ; Cornell University [New York] ; Université Pierre et Marie Curie - Paris 6 (UPMC) ; Università degli Studi dell'Aquila = University of L'Aquila (UNIVAQ) |
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| Quelle: | Advances in Quantum Chemistry Advances in Quantum Chemistry, Elsevier, 2017, Novel Electronic Structure Theory: General Innovations and Strongly Correlated Systems Advances in Quantum Chemistry, 2017, Novel Electronic Structure Theory: General Innovations and Strongly Correlated Systems; (2017) |
| Veröffentlichung: | 2017 |
| Medientyp: | unknown |
| ISSN: | 0065-3276 (print) |
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