Related papers: Excited State Specific Multi-Slater Jastrow Wave F…
We present a method for finding individual excited states' energy stationary points in complete active space self-consistent field theory that is compatible with standard optimization methods and highly effective at overcoming difficulties…
A quantum Monte Carlo method is presented for determining multi-determinantal Jastrow-Slater wave functions for which the energy is stationary with respect to the simultaneous optimization of orbitals and configuration interaction…
State-specific electronic structure theory provides a route towards balanced excited-state wave functions by exploiting higher-energy stationary points of the electronic energy. Multiconfigurational wave function approximations can describe…
We employ quantum Monte Carlo to obtain chemically accurate vertical and adiabatic excitation energies, and equilibrium excited-state structures for the small, yet challenging, formaldehyde and thioformaldehyde molecules. A key ingredient…
It is proven that the exact excited-state wave function and energy may be obtained by minimizing the energy expectation value of trial wave functions that are constrained only to have the correct nodes of the state of interest. This…
We present a variational function that targets excited states directly based on their position in the energy spectrum, along with a Monte Carlo method for its evaluation and minimization whose cost scales polynomially for a wide class of…
We employ a generalized variational principle to improve the stability, reliability, and precision of fully excited-state-specific complete active space self-consistent field theory. Compared to previous approaches that similarly seek to…
We demonstrate that, rather than resorting to high-cost dynamic correlation methods, qualitative failures in excited-state potential energy surface predictions can often be remedied at no additional cost by ensuring that optimal molecular…
In the regime where traditional approaches to electronic structure cannot afford to achieve accurate energy differences via exhaustive wave function flexibility, rigorous approaches to balancing different states' accuracies become…
Variational calculations of excited electronic states are carried out by finding saddle points on the surface that describes how the energy of the system varies as a function of the electronic degrees of freedom. This approach has several…
We present an excited-state-specific coupled-cluster approach in which both the molecular orbitals and cluster amplitudes are optimized for an individual excited state. The theory is formulated via a pseudoprojection of the traditional…
Variational optimization of orbitals in time-independent density functional calculations of excited electronic states presents a significant challenge, as excited states typically correspond to saddle points on the electronic energy…
The development of variational density functional theory approaches to excited electronic states is impeded by limitations of the commonly used self-consistent field (SCF) procedure. A method based on a direct optimization approach as well…
Excited states in molecules can be difficult to investigate and generally require methods that are either computationally expensive or are not universally accurate. Recent research has focused on using higher-energy Slater determinants as…
State-specific complete active space self-consistent field (SS-CASSCF) theory has emerged as a promising route to accurately predict electronically excited energy surfaces away from molecular equilibria. However, its accuracy and…
We present a simple and efficient wave function ansatz for the treatment of excited charge-transfer states in real-space quantum Monte Carlo methods. Using the recently-introduced variation-after-response method [J. Chem. Phys. 145, 081103…
We show that it is possible to describe the ground state of the Luttinger model in terms of a Jastrow-Slater wave function. Moreover, our findings reveal that one-particle excitations and their corresponding dynamics can be faithfully…
We investigate an extension of excited state mean-field theory in which the energy expression is augmented with density functional components in an effort to include the effects of weak electron correlations. The approach remains…
We present a first principles strategy for developing state-specific density functional approximations for excited states. We first clarify why approaches based on conventional ground state approximations miss density-driven correlations,…
We present a generalization of the variational principle that is compatible with any Hamiltonian eigenstate that can be specified uniquely by a list of properties. This variational principle appears to be compatible with a wide range of…