Time-dependent linear-response variational Monte Carlo
arXiv:1705.09813 · doi:10.1016/bs.aiq.2017.05.005
Abstract
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
References in corpus (4)
- Jastrow correlation factor for atoms, molecules, and solids
- Full optimization of Jastrow-Slater wave functions with application to the first-row atoms and homonuclear diatomic molecules
- Static and dynamical correlation in diradical molecules by Quantum Monte Carlo using the Jastrow Antisymmetrized Geminal Power ansatz
- Variation After Response in Quantum Monte Carlo
Cited by in corpus (5)
- QMCPACK: Advances in the development, efficiency, and application of auxiliary field and real-space variational and diffusion Quantum Monte Carlo
- Solving Quasiparticle Band Spectra of Real Solids using Neural-Network Quantum States
- All-electron quantum Monte Carlo with Jastrow single determinant Ansatz: application to the sodium dimer
- Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo
- Basis-set correction based on density-functional theory: Linear-response formalism for excited-state energies