2021
DOI: 10.1021/acs.jpca.0c11356
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Electrostatics, Charge Transfer, and the Nature of the Halide–Water Hydrogen Bond

Abstract: Binary halide-water complexes X − (H2O) are examined by means of symmetry-adapted perturbation theory, using charge-constrained promolecular reference densities to extract a meaningful chargetransfer component from the induction energy. As is known, the X − (H2O) potential energy surface (for X = F, Cl, Br, or I) is characterized by symmetric left and right hydrogen bonds separated by a C2v-symmetric saddle point, with a tunneling barrier height that is < 2 kcal/mol except in the case of F − (H2O). Our analysi… Show more

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Cited by 25 publications
(61 citation statements)
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References 118 publications
(348 reference statements)
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“…Because the SCF procedure is variational, lifting of this constraint necessarily lowers the energy (to that of the fully-relaxed SCF solution), and this energy lowering is taken to define E CT . The CT energy thus obtained is then subtracted from the induction energy to obtain the CT-free polarization energy, E pol = E ind − E CT [64,[66][67][68]. CT energies defined in this way are very nearly converged already in double-ζ basis sets [64].…”
Section: Polarization and Charge Transfermentioning
confidence: 99%
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“…Because the SCF procedure is variational, lifting of this constraint necessarily lowers the energy (to that of the fully-relaxed SCF solution), and this energy lowering is taken to define E CT . The CT energy thus obtained is then subtracted from the induction energy to obtain the CT-free polarization energy, E pol = E ind − E CT [64,[66][67][68]. CT energies defined in this way are very nearly converged already in double-ζ basis sets [64].…”
Section: Polarization and Charge Transfermentioning
confidence: 99%
“…CT energies defined in this way are very nearly converged already in double-ζ basis sets [64]. This approach has previously been used to demonstrate that E CT furnishes a driving force for formation of quasi-linear hydrogen bonds in binary halide-water complexes [52,68]. Implementation of the charge-constrained SCF procedure requires a method to count electrons, and Becke's multicenter partition scheme [69] is commonly used for this purpose [65].…”
Section: Polarization and Charge Transfermentioning
confidence: 99%
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