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Communication: GAIMS—Generalized Ab Initio
Multiple Spawning for both internal conversion and intersystem crossing processes
1.C. M. Marian, “Spin-orbit coupling and intersystem crossing in molecules,” Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2, 187–203 (2012).
3.M. Richter, P. Marquetand, J. González-Vázquez, I. Sola, and L. González, “Femtosecond intersystem crossing in the DNA nucleobase cytosine,” J. Phys. Chem. Lett. 3(21), 3090–3095 (2012).
4.L. Martínez-Fernández, I. Corral, G. Granucci, and M. Persico, “Competing ultrafast intersystem crossing and internal conversion: A time resolved picture for the deactivation of 6-thioguanine,” Chem. Sci. 5, 1336 (2014).
5.M. Chergui, “On the interplay between charge, spin and structural dynamics in transition metal complexes,” Dalton Trans. 41(42), 13022–13029 (2012).
6.H. Yersin, A. F. Rausch, R. Czerwieniec, T. Hofbeck, and T. Fischer, “The triplet state of organo-transition metal compounds. Triplet harvesting and singlet harvesting for efficient OLEDs,” Coord. Chem. Rev. 255(21), 2622–2652 (2011).
7.T. Kinoshita, J. T. Dy, S. Uchida, T. Kubo, and H. Segawa, “Wideband dye-sensitized solar cells employing a phosphine-coordinated ruthenium sensitizer,” Nat. Photonics 7(7), 535–539 (2013).
8.M. C. Heitz, C. Ribbing, and C. Daniel, “Spin-orbit induced radiationless transitions in organometallics: Quantum simulation of the intersystem crossing processes in the photodissociation of HCo(CO)4,” J. Chem. Phys. 106(4), 1421–1428 (1997).
9.M. Persico and G. Granucci, “An overview of nonadiabatic dynamics simulations methods, with focus on the direct approach versus the fitting of potential energy surfaces,” Theor. Chem. Acc. 133, 1526 (2014).
10.R. S. Minns, D. S. N. Parker, T. J. Penfold, G. A. Worth, and H. H. Fielding, “Competing ultrafast intersystem crossing and internal conversion in the ‘channel 3’ region of benzene,” Phys. Chem. Chem. Phys. 12(48), 15607–15615 (2010).
11.M. Richter, P. Marquetand, J. González-Vázquez, I. Sola, and L. González, “SHARC: Ab initio molecular dynamics with surface hopping in the adiabatic representation including arbitrary couplings,” J. Chem. Theory Comput. 7, 1253–1258 (2011).
12.B. N. Fu, B. C. Shepler, and J. M. Bowman, “Three-state trajectory surface hopping studies of the photodissociation dynamics of formaldehyde on ab initio potential energy surfaces,” J. Am. Chem. Soc. 133(20), 7957–7968 (2011).
13.G. Granucci, M. Persico, and G. Spighi, “Surface hopping trajectory simulations with spin-orbit and dynamical couplings,” J. Chem. Phys. 137(22), 22A501 (2012).
14.G. L. Cui and W. Thiel, “Generalized trajectory surface-hopping method for internal conversion and intersystem crossing,” J. Chem. Phys. 141(12), 124101 (2014).
15.F. F. de Carvalho and I. Tavernelli, “Nonadiabatic dynamics with intersystem crossings: A time-dependent density functional theory implementation,” J. Chem. Phys. 143(22), 224105 (2015).
16.S. Mai, P. Marquetand, and L. Gonzalez, “A general method to describe intersystem crossing dynamics in trajectory surface hopping,” Int. J. Quantum Chem. 115(18), 1215–1231 (2015).
17.K. Rajak and B. Maiti, “Trajectory surface hopping study of theO(3P) + C2H2 reaction dynamics: Effect of collision energy on the extent of intersystem crossing,” J. Chem. Phys. 140(4), 044314 (2014).
18.G. Granucci and M. Persico, “Critical appraisal of the fewest switches algorithm for surface hopping,” J. Chem. Phys. 126, 134114 (2007).
20.M. Ben-Nun and T. J. Martínez, “Nonadiabatic molecular dynamics: Validation of the multiple spawning method for a multidimensional problem,” J. Chem. Phys. 108(17), 7244–7257 (1998).
21.T. J. Martínez, M. Ben-Nun, and R. D. Levine, “Multi-electronic-state molecular dynamics: A wave function approach with applications,” J. Phys. Chem. 100(19), 7884–7895 (1996).
23.M. Ben-Nun, J. Quenneville, and T. J. Martínez, “Ab initio multiple spawning: Photochemistry from first principles quantum molecular dynamics,” J. Phys. Chem. A 104(22), 5161–5175 (2000).
24.S. Yang and T. J. Martínez, “Ab initio multiple spawning: First principles dynamics around conical intersections,” in Conical Intersections: Theory, Computation and Experiment, edited by W. Domcke, D. R. Yarkony, and H. Köppel (World Scientific Publishing Co. Pte. Ltd., 2011), Vol. 17, pp. 347–374.
25.J. Almlöf and O. Gropen, “Relativistic effects in chemistry,” in Reviews in Computational Chemistry, edited by K. B. Lipkowitz and D. B. Boyd (VCH Publishers, New York, 1996), Vol. 8, p. 203.
26.The additional terms in the Breit-Pauli Hamiltonian are not considered here.
27.D. G. Fedorov, S. Koseki, M. W. Schmidt, and M. S. Gordon, “Spin-orbit coupling in molecules: Chemistry beyond the adiabatic approximation,” Int. Rev. Phys. Chem. 22(3), 551–592 (2003).
28.M. Dolg and X. Y. Cao, “Relativistic pseudopotentials: Their development and scope of applications,” Chem. Rev. 112(1), 403–480 (2012).
30.M. Reiher and A. Wolf, Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science (Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2009).
31.K. G. Dyall and J. Knut Fægri, Introduction to Relativistic Quantum Chemistry (Oxford University Press, Inc., New York, 2007).
32.M. Born and K. Huang, Dynamical Theory of Crystal Lattices (Clarendon, Oxford, 1954).
33.G. A. Worth, M. A. Robb, and B. Lasorne, “Solving the time-dependent Schrödinger equation for nuclear motion in one step: Direct dynamics of non-adiabatic systems,” Mol. Phys. 106(16-18), 2077–2091 (2008).
34.D. V. Shalashilin, “Quantum mechanics with the basis set guided by Ehrenfest trajectories: Theory and application to spin-boson model,” J. Chem. Phys. 130, 244101 (2009).
35.S. Yang, J. D. Coe, B. Kaduk, and T. J. Martínez, “An ‘optimal’ spawning algorithm for adaptive basis set expansion in nonadiabatic dynamics,” J. Chem. Phys. 130(13), 134113 (2009).
36.In the absence of an external magnetic field, the sublevels of a given electronic state with S > 0 are exactly degenerate. Therefore, the TBFs for different sublevels resulting from a given spawning event will follow the very same classical trajectory, implying that the corresponding complex coefficients can be evolved on the support of only one trajectory as shown in Figure 2. This observation leads to substantial computational savings for the propagation of the Gaussian functions. There is no approximation involved since all sublevel coefficients are still explicitly considered and time-evolved.
37.M. Sulc, H. Hernandez, T. J. Martínez, and J. Vanicek, “Relation of exact Gaussian basis methods to the dephasing representation: Theory and application to time-resolved electronic spectra,” J. Chem. Phys. 139(3), 034112 (2013).
38.T. J. Martínez and R. D. Levine, “Non-adiabatic molecular dynamics: Split-operator multiple spawning with applications to photodissociation,” J. Chem. Soc., Faraday Trans. 93(5), 941–947 (1997).
41.H. J. Werner, P. J. Knowles, G. Knizia, F. R. Manby, and M. Schutz, “ molpro: A general-purpose quantum chemistry program package,” Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2(2), 242–253 (2012).
42.L. Favero, G. Granucci, and M. Persico, “Dynamics of acetone photodissociation: A surface hopping study,” Phys. Chem. Chem. Phys. 15(47), 20651–20661 (2013).
43.E. G. Hohenstein, N. Luehr, I. S. Ufimtsev, and T. J. Martínez, “An atomic orbital-based formulation of the complete active space self-consistent field method on graphical processing units,” J. Chem. Phys. 142(22), 224103 (2015).
44.J. W. Snyder, E. G. Hohenstein, N. Luehr, and T. J. Martínez, “An atomic orbital-based formulation of analytical gradients and nonadiabatic coupling vector elements for the state-averaged complete active space self-consistent field method on graphical processing units,” J. Chem. Phys. 143(15), 154107 (2015).
45.E. G. Hohenstein, M. E. F. Bouduban, C. C. Song, N. Luehr, I. S. Ufimtsev, and T. J. Martínez, “Analytic first derivatives of floating occupation molecular orbital-complete active space configuration interaction on graphical processing units,” J. Chem. Phys. 143(1), 014111 (2015).
46.B. S. Fales and B. G. Levine, “Nanoscale multireference quantum chemistry: Full configuration interaction on graphical processing units,” J. Chem. Theory Comput. 11(10), 4708–4716 (2015).
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Full multiple spawning is a formally exact method to describe the excited-statedynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation.
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