期刊
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
卷 14, 期 9, 页码 4590-4599出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.8b00337
关键词
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资金
- Engineering and Physical Sciences Research Council (EPSRC) Centre for Doctoral Training in Theory and Modelling in Chemical Sciences [EPSRC EP/L015722/1]
We present Unsold-W12 (UW12), an approximation to the correlation energy of molecules that is an explicit functional of the single-particle reduced-density matrix. The approximation resembles one part of modern explicitly correlated second-order Moller-Plesset (MP2) theory and is intended as an alternative to MP2 in double-hybrid exchange-correlation functionals. Orbital optimization with UW12 is straightforward, and the UW12 energy is evaluated without a double summation over unoccupied orbitals, leading to a faster basis-set convergence than is seen in double-hybrid functionals. We suggest a one-parameter hybrid exchange-correlation functional XCH-BLYP-UW12. XCH-BLYP-UW12 is similar to double-hybrid functionals, but contains UW12 correlation instead of MP2 correlation. We find that XCH-BLYP-UW12 is more accurate than the existing double-hybrid functional B2-PLYP for small-molecule main-group reaction barrier heights and has roughly the same accuracy as the existing hybrid functional B3LYP for atomization energies.
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