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Volumn 119, Issue 15, 2003, Pages 7672-7684

Efficient real-space configuration-interaction method for the simulation of multielectron mixed quantum and classical nonadiabatic molecular dynamics in the condensed phase

Author keywords

[No Author keywords available]

Indexed keywords

DEGREES OF FREEDOM (MECHANICS); ELECTRONS; MOLECULAR DYNAMICS; POTENTIAL ENERGY;

EID: 0242352597     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.1610438     Document Type: Article
Times cited : (17)

References (73)
  • 5
    • 36749113388 scopus 로고
    • E. J. Heller, J. Chem. Phys. 62, 1544 (1975); 75, 2923 (1981).
    • (1981) J. Chem. Phys. , vol.75 , pp. 2923
  • 6
    • 0036083594 scopus 로고    scopus 로고
    • G. D. Billing, Phys. Chem. Chem. Phys. 4, 2865 (2002); Chem. Phys. Lett. 343, 130 (2001); C. Coletti and G. D. Billing, ibid. 368, 289 (2003).
    • (2002) Phys. Chem. Chem. Phys. , vol.4 , pp. 2865
    • Billing, G.D.1
  • 7
    • 0000415695 scopus 로고    scopus 로고
    • G. D. Billing, Phys. Chem. Chem. Phys. 4, 2865 (2002); Chem. Phys. Lett. 343, 130 (2001); C. Coletti and G. D. Billing, ibid. 368, 289 (2003).
    • (2001) Chem. Phys. Lett. , vol.343 , pp. 130
  • 8
    • 0037449392 scopus 로고    scopus 로고
    • G. D. Billing, Phys. Chem. Chem. Phys. 4, 2865 (2002); Chem. Phys. Lett. 343, 130 (2001); C. Coletti and G. D. Billing, ibid. 368, 289 (2003).
    • (2003) Chem. Phys. Lett. , vol.368 , pp. 289
    • Coletti, C.1    Billing, G.D.2
  • 14
    • 33751158459 scopus 로고
    • B. J. Schwartz and P. J. Rossky, J. Phys. Chem. 98, 4489 (1994); 99, 2953 (1995); J. Chem. Phys. 101, 6902 (1994); 101, 6917 (1994); Phys. Rev. Lett. 72, 3282 (1994); J. Mol. Liq. 65-66, 23 (1995); B. J. Schwartz, E. R. Bittner, O. V. Prezhdo, and P. J. Rossky, J. Chem. Phys. 104, 5942 (1996).
    • (1994) J. Phys. Chem. , vol.98 , pp. 4489
    • Schwartz, B.J.1    Rossky, P.J.2
  • 15
    • 33751156494 scopus 로고
    • B. J. Schwartz and P. J. Rossky, J. Phys. Chem. 98, 4489 (1994); 99, 2953 (1995); J. Chem. Phys. 101, 6902 (1994); 101, 6917 (1994); Phys. Rev. Lett. 72, 3282 (1994); J. Mol. Liq. 65-66, 23 (1995); B. J. Schwartz, E. R. Bittner, O. V. Prezhdo, and P. J. Rossky, J. Chem. Phys. 104, 5942 (1996).
    • (1995) J. Phys. Chem. , vol.99 , pp. 2953
  • 16
    • 0008960224 scopus 로고
    • B. J. Schwartz and P. J. Rossky, J. Phys. Chem. 98, 4489 (1994); 99, 2953 (1995); J. Chem. Phys. 101, 6902 (1994); 101, 6917 (1994); Phys. Rev. Lett. 72, 3282 (1994); J. Mol. Liq. 65-66, 23 (1995); B. J. Schwartz, E. R. Bittner, O. V. Prezhdo, and P. J. Rossky, J. Chem. Phys. 104, 5942 (1996).
    • (1994) J. Chem. Phys. , vol.101 , pp. 6902
  • 17
    • 0008892324 scopus 로고
    • B. J. Schwartz and P. J. Rossky, J. Phys. Chem. 98, 4489 (1994); 99, 2953 (1995); J. Chem. Phys. 101, 6902 (1994); 101, 6917 (1994); Phys. Rev. Lett. 72, 3282 (1994); J. Mol. Liq. 65-66, 23 (1995); B. J. Schwartz, E. R. Bittner, O. V. Prezhdo, and P. J. Rossky, J. Chem. Phys. 104, 5942 (1996).
    • (1994) J. Chem. Phys. , vol.101 , pp. 6917
  • 18
    • 0010063693 scopus 로고
    • B. J. Schwartz and P. J. Rossky, J. Phys. Chem. 98, 4489 (1994); 99, 2953 (1995); J. Chem. Phys. 101, 6902 (1994); 101, 6917 (1994); Phys. Rev. Lett. 72, 3282 (1994); J. Mol. Liq. 65-66, 23 (1995); B. J. Schwartz, E. R. Bittner, O. V. Prezhdo, and P. J. Rossky, J. Chem. Phys. 104, 5942 (1996).
    • (1994) Phys. Rev. Lett. , vol.72 , pp. 3282
  • 19
    • 33751158459 scopus 로고
    • B. J. Schwartz and P. J. Rossky, J. Phys. Chem. 98, 4489 (1994); 99, 2953 (1995); J. Chem. Phys. 101, 6902 (1994); 101, 6917 (1994); Phys. Rev. Lett. 72, 3282 (1994); J. Mol. Liq. 65-66, 23 (1995); B. J. Schwartz, E. R. Bittner, O. V. Prezhdo, and P. J. Rossky, J. Chem. Phys. 104, 5942 (1996).
    • (1995) J. Mol. Liq. , vol.65-66 , pp. 23
  • 20
    • 0030126484 scopus 로고    scopus 로고
    • B. J. Schwartz and P. J. Rossky, J. Phys. Chem. 98, 4489 (1994); 99, 2953 (1995); J. Chem. Phys. 101, 6902 (1994); 101, 6917 (1994); Phys. Rev. Lett. 72, 3282 (1994); J. Mol. Liq. 65-66, 23 (1995); B. J. Schwartz, E. R. Bittner, O. V. Prezhdo, and P. J. Rossky, J. Chem. Phys. 104, 5942 (1996).
    • (1996) J. Chem. Phys. , vol.104 , pp. 5942
    • Schwartz, B.J.1    Bittner, E.R.2    Prezhdo, O.V.3    Rossky, P.J.4
  • 32
  • 33
    • 0037088365 scopus 로고    scopus 로고
    • K. F. Wong and P. J. Rossky, J. Phys. Chem. A 105, 2546 (2001); J. Chem. Phys. 116, 8418 (2002); 116, 8429 (2002).
    • (2002) J. Chem. Phys. , vol.116 , pp. 8418
  • 34
    • 0037088354 scopus 로고    scopus 로고
    • K.F. Wong and P. J. Rossky, J. Phys. Chem. A 105, 2546 (2001); 116, 8418 (2002); 116, 8429 (2002).
    • (2002) J. Chem. Phys. , vol.116 , pp. 8429
  • 37
    • 3843142910 scopus 로고
    • J. Schnitker, K. Motakabbir, P. J. Rossky, and R. Friesner, Phys. Rev. Lett. 60, 456 (1988); D. Borgis and A. Staib, Chem. Phys. Lett. 230, 405 (1994) ; D. Borgis and S. Bratos, J. Mol. Struct. 437, 537 (1997); C. Nicolas, A, Boutin, B. Lévy, and D. Borgis, J. Chem. Phys. 118, 9689 (2003).
    • (1988) Phys. Rev. Lett. , vol.60 , pp. 456
    • Schnitker, J.1    Motakabbir, K.2    Rossky, P.J.3    Friesner, R.4
  • 38
    • 11644266170 scopus 로고
    • J. Schnitker, K. Motakabbir, P. J. Rossky, and R. Friesner, Phys. Rev. Lett. 60, 456 (1988); D. Borgis and A. Staib, Chem. Phys. Lett. 230, 405 (1994) ; D. Borgis and S. Bratos, J. Mol. Struct. 437, 537 (1997); C. Nicolas, A, Boutin, B. Lévy, and D. Borgis, J. Chem. Phys. 118, 9689 (2003).
    • (1994) Chem. Phys. Lett. , vol.230 , pp. 405
    • Borgis, D.1    Staib, A.2
  • 39
    • 10044267627 scopus 로고    scopus 로고
    • J. Schnitker, K. Motakabbir, P. J. Rossky, and R. Friesner, Phys. Rev. Lett. 60, 456 (1988); D. Borgis and A. Staib, Chem. Phys. Lett. 230, 405 (1994) ; D. Borgis and S. Bratos, J. Mol. Struct. 437, 537 (1997); C. Nicolas, A, Boutin, B. Lévy, and D. Borgis, J. Chem. Phys. 118, 9689 (2003).
    • (1997) J. Mol. Struct. , vol.437 , pp. 537
    • Borgis, D.1    Bratos, S.2
  • 40
    • 0037665235 scopus 로고    scopus 로고
    • J. Schnitker, K. Motakabbir, P. J. Rossky, and R. Friesner, Phys. Rev. Lett. 60, 456 (1988); D. Borgis and A. Staib, Chem. Phys. Lett. 230, 405 (1994) ; D. Borgis and S. Bratos, J. Mol. Struct. 437, 537 (1997); C. Nicolas, A, Boutin, B. Lévy, and D. Borgis, J. Chem. Phys. 118, 9689 (2003).
    • (2003) J. Chem. Phys. , vol.118 , pp. 9689
    • Nicolas, C.1    Boutin, A.2    Lévy, B.3    Borgis, D.4
  • 41
    • 0242291480 scopus 로고    scopus 로고
    • An overview of the configuration interaction method can be found in Chap. 4 of Ref. 20
    • An overview of the configuration interaction method can be found in Chap. 4 of Ref. 20
  • 42
    • 0242323125 scopus 로고    scopus 로고
    • note
    • 12 cannot, of course, be represented as a direct product of single-electron operators: interactions between the electrons will not be diagonal in a one-electron basis.
  • 43
    • 0242323127 scopus 로고    scopus 로고
    • note
    • Because the Coulomb interaction does not affect the spin of an electron, spin flips can only be induced by terms in the electron-solvent Hamiltonians (e.g., by magnetic fields induced by moving charges in the solvent) or by direct spin-spin interactions. In this work, we will neglect such spin interactions, but we note that the extension to such cases is straightfor-ward.
  • 45
    • 0242291479 scopus 로고    scopus 로고
    • note
    • ij results from the symmetry of the cubic lattice.
  • 46
    • 0242291482 scopus 로고    scopus 로고
    • note
    • -8, therefore, we can use our tabulated values to compute ø between cubes within 16 grid points of each other, approximating all other values of ø by 1/r.
  • 49
    • 0242291478 scopus 로고
    • N. Basco, G. A. Kenney, and D. C. Walker, Chem. Commun. 917 (1969); N. Basco, G. A. Kenney-Wallace, S. K. Vidyarthi, and D. C. Walker, Can. J. Chem. 50, 2059 (1972); D. Meisel, G. Czapski, M. S. Matheson, and W. A. Mulac, Int. J. Radiat. Phys. Chem. 7, 233 (1975).
    • (1969) Chem. Commun. , vol.917
    • Basco, N.1    Kenney, G.A.2    Walker, D.C.3
  • 50
    • 0242291481 scopus 로고
    • N. Basco, G. A. Kenney, and D. C. Walker, Chem. Commun. 917 (1969); N. Basco, G. A. Kenney-Wallace, S. K. Vidyarthi, and D. C. Walker, Can. J. Chem. 50, 2059 (1972); D. Meisel, G. Czapski, M. S. Matheson, and W. A. Mulac, Int. J. Radiat. Phys. Chem. 7, 233 (1975).
    • (1972) Can. J. Chem. , vol.50 , pp. 2059
    • Basco, N.1    Kenney-Wallace, G.A.2    Vidyarthi, S.K.3    Walker, D.C.4
  • 51
    • 0242354487 scopus 로고
    • N. Basco, G. A. Kenney, and D. C. Walker, Chem. Commun. 917 (1969); N. Basco, G. A. Kenney-Wallace, S. K. Vidyarthi, and D. C. Walker, Can. J. Chem. 50, 2059 (1972); D. Meisel, G. Czapski, M. S. Matheson, and W. A. Mulac, Int. J. Radiat. Phys. Chem. 7, 233 (1975).
    • (1975) Int. J. Radiat. Phys. Chem. , vol.7 , pp. 233
    • Meisel, D.1    Czapski, G.2    Matheson, M.S.3    Mulac, W.A.4
  • 55
    • 4143153789 scopus 로고
    • Z. H. Deng, G. J. Martyna, and M. L. Klein, Phys. Rev. Lett. 68, 2496 (1992); 71, 267 (1993); J. Chem. Phys. 100, 7590 (1994); G. J. Martyna, Z. H. Deng, and M. L. Klein, ibid. 98, 555 (1993).
    • (1992) Phys. Rev. Lett. , vol.68 , pp. 2496
    • Deng, Z.H.1    Martyna, G.J.2    Klein, M.L.3
  • 56
    • 7044257547 scopus 로고
    • Z. H. Deng, G. J. Martyna, and M. L. Klein, Phys. Rev. Lett. 68, 2496 (1992); 71, 267 (1993); J. Chem. Phys. 100, 7590 (1994); G. J. Martyna, Z. H. Deng, and M. L. Klein, ibid. 98, 555 (1993).
    • (1993) Phys. Rev. Lett. , vol.71 , pp. 267
  • 57
    • 36449009423 scopus 로고
    • Z. H. Deng, G. J. Martyna, and M. L. Klein, Phys. Rev. Lett. 68, 2496 (1992); 71, 267 (1993); J. Chem. Phys. 100, 7590 (1994); G. J. Martyna, Z. H. Deng, and M. L. Klein, ibid. 98, 555 (1993).
    • (1994) J. Chem. Phys. , vol.100 , pp. 7590
  • 58
    • 0000161744 scopus 로고
    • Z. H. Deng, G. J. Martyna, and M. L. Klein, Phys. Rev. Lett. 68, 2496 (1992); 71, 267 (1993); J. Chem. Phys. 100, 7590 (1994); G. J. Martyna, Z. H. Deng, and M. L. Klein, ibid. 98, 555 (1993).
    • (1993) J. Chem. Phys. , vol.98 , pp. 555
    • Martyna, G.J.1    Deng, Z.H.2    Klein, M.L.3
  • 61
    • 0003570366 scopus 로고
    • revised ed. (Addison-Wesley, Reading, MA,), Chap. 2
    • J. J. Sakurai, Modern Quantum Mechanics, revised ed. (Addison-Wesley, Reading, MA, 1994), Chap. 2.
    • (1994) Modern Quantum Mechanics
    • Sakurai, J.J.1
  • 62
    • 0242291474 scopus 로고    scopus 로고
    • note
    • We define energy conservation by requiring any long-term drift in the total energy to be within the rms fluctuation over the course of a 2 ps run. The rms energy fluctuation is 0.08 eV for △t = 1.0 and 0.02 eV for △t = 0.5fs.
  • 63
    • 0242291476 scopus 로고    scopus 로고
    • note
    • update= 4 fs criterion is actually overly generous.
  • 65
    • 0242354480 scopus 로고    scopus 로고
    • note
    • A simple uncertainty-principle argument shows that the kinetic energy reduction associated with going from a cavity 4.0 Å in diameter to one 4. 8 Å in diameter is less than ∼0.1 eV.
  • 66
    • 0242354483 scopus 로고    scopus 로고
    • note
    • This change of shape from an "s-like" symmetry to a "p-like" symmetry is similar to what happens when a single hydrated electron is excited (see Refs. 9, 11, and 23), so it is not suprising that the time scale and mechanism of the Stokes shift are similar for the hydrated electron and the singlet dielectron.
  • 67
    • 0242323121 scopus 로고    scopus 로고
    • note
    • The two cavities of the excited state dielectron cannot properly be thought of as two separated single electrons because the exchange energy of ∼0.5 eV indicates that each one-electron basis state has amplitude in both holes.
  • 68
    • 0242385977 scopus 로고    scopus 로고
    • note
    • i). At first glance, the latter term appears quite similar to the Pulay force (Ref. 51) that corrects the Hellmann-Feynman force when the basis functions used to describe the quantum system vary with, e.g., nuclear postion. A difference between the adiabatic and nonadiabatic cases, however, is that this nonadiabatic "Pulay-type" term comes from changes in the adiabatic expansion coefficients rather than from changes in the basis. Unlike the Pulay force, therefore, the time dependence of the CI expansion coefficients is physically meaningful, and does not vanish in the limit that the basis set (here |nm〉±) is complete.
  • 69
    • 0242385975 scopus 로고    scopus 로고
    • note
    • i〉) = 0, applying the product rule for derivatives and integrating by parts once.
  • 70
    • 0242323120 scopus 로고
    • edited by H. F. Schaefer III (Plenum, New York)
    • P. Pulay, in Applications of Electronic Structure Theory, edited by H. F. Schaefer III (Plenum, New York, 1977); M. Di Ventra and S. T. Pantelides, Phys. Rev. B 61, 16207 (2000).
    • (1977) Applications of Electronic Structure Theory
    • Pulay, P.1
  • 71
    • 0004945383 scopus 로고    scopus 로고
    • P. Pulay, in Applications of Electronic Structure Theory, edited by H. F. Schaefer III (Plenum, New York, 1977); M. Di Ventra and S. T. Pantelides, Phys. Rev. B 61, 16207 (2000).
    • (2000) Phys. Rev. B , vol.61 , pp. 16207
    • Di Ventra, M.1    Pantelides, S.T.2
  • 72
    • 0242354482 scopus 로고    scopus 로고
    • note
    • One difference between the usual single-electron force and that for our CI case is that the CI expansion coefficients change in time. This change gives rise to a correction to the HF force, the Pulay force, Ref. 51, whenever a finite CI basis set is used (as will always be the case in practice). The specific form of the Pulay force for CI wave functions is straightfor-ward, though tedious, to derive using first-order perturbation theory and the approach of Di Ventra and Pantelides (Ref. 51). We have examined the Pulay force for the hydrated dielectron system discussed in Sec. IV and found it to be negligible in comparison to the HF forces themselves, so we do not bother to explicitly display it here.


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