Toward a Balanced Description of Ground and Excited States with Transcorrelated F12 Methods
Conner Masteran, Bimal Gaudel, Edward F. Valeev
TL;DR
This paper introduces a new method to better describe both ground and excited states in quantum chemistry calculations.
Contribution
The novel approach extends F12 correlators to occupied and valence unoccupied orbitals, achieving balanced ground and excited state descriptions.
Findings
The new F12 geminal design avoids unphysical raising of ground-state energy.
The method reduces basis set requirements for accurate ground and excited state calculations.
It improves description of CCSD energies, excitation energies, and vibrational frequencies.
Abstract
By correlating only the 1-particle states occupied in the reference determinant, the conventional design for the single-reference R12/F12 explicitly correlated methods biases them toward the ground-state description, thereby making the treatment of response properties of the ground state, and energies and other properties of excited states less robust. While the use of multireference methods and/or extensions of the standard SP-projected geminals can achieve a more balanced description of ground and excited states, here we show that the same goals can be achieved by extending the action of F12 correlators to the occupied and valence unoccupied 1-particle states only. This design choice reflects the strong dependence of the optimal correlation length scale of the F12 ansatz on the orbital energies/structure, and helps to avoid the unphysical raising of the ground-state energy if the F12…
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Taxonomy
TopicsAdvanced Chemical Physics Studies · Atmospheric Ozone and Climate · Spectroscopy and Quantum Chemical Studies