期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 120, 期 47, 页码 12148-12159出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.6b09176
关键词
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资金
- American Chemical Society Petroleum Research Fund [53674-DNI6]
- Department of Energy, Office of Basic Energy Sciences CTC program [DE-SC0014437]
- Department of Energy, Office of Basic Energy Sciences CPIMS program [DE-SC0014437]
- University of California
- ACS Project SEED program
- National Science Foundation [ACI-1429783]
- Office of Advanced Cyberinfrastructure (OAC)
- Direct For Computer & Info Scie & Enginr [1429783] Funding Source: National Science Foundation
Mixed quantum mechanical (QM)/classical methods provide a computationally efficient approach to modeling both ground and excited states in the condensed phase. To accurately model short-range interactions, some amount of the environment can be included in the QM region, whereas a classical model can treat long-range interactions to maintain computational affordability. The best computational protocol for these mixed QM/classical methods can be determined by examining convergence of molecular properties. Here, we compare molecular mechanical (MM) fixed point charges to a polarizable continuum model (PCM) for computing electronic excitations in solution. We computed the excitation energy of three pairs of neutral/anionic molecules in aqueous solvent, including up to 250 water molecules in the QM region. Interestingly, the convergence is similar for MM point charges and a PCM, with convergence achieved when at least one full solvation shell is treated with QM. Although the van der Waals (VDW) definition of the PCM cavity is adequate with small amounts of QM solvent, larger QM solvent layers had gaps in the VDW PCM cavity, leading to asymptotically incorrect excitation energies. Given that the VDW cavity leads to unphysical solutesolvent interactions, we advise using a solvent-excluded surface cavity for QM/PCM calculations that include QM solvent.
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