Excited-State Geometry Optimization of Small Molecules with Many-Body Green’s Functions Theory
نویسندگان
چکیده
We present a benchmark study of gas phase geometry optimizations in the excited states carbon monoxide, acetone, acrolein, and methylenecyclopropene using many-body Green’s functions theory within GW approximation Bethe–Salpeter equation (BSE) employing numerical gradients. scrutinize influence several typical approximations GW-BSE framework; we used one-shot G0W0 or eigenvalue self-consistent evGW, fully analytic approach plasmon-pole model for frequency dependence electron self-energy, performing BSE step Tamm–Dancoff approximation. The obtained geometries are compared to reference results from multireference perturbation (CASPT2), variational Monte Carlo (VMC) method, second-order approximate coupled cluster (CC2) time-dependent density-functional (TDDFT). find overall good agreement structural parameters optimized with calculations CASPT2, an average relative error around 1% 1.5% evGW variants based on PBE0 ground state, respectively, while other have negligible influence. errors also smaller than those CC2 TDDFT different functionals only larger VMC, indicating that method does not yield excitation energies but established higher-order wave function methods.
منابع مشابه
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ژورنال
عنوان ژورنال: Journal of Chemical Theory and Computation
سال: 2021
ISSN: ['1549-9618', '1549-9626']
DOI: https://doi.org/10.1021/acs.jctc.0c01099