Hybrid quantum/classical simulation of the vibrational relaxation of the bend fundamental in liquid water

被引:15
作者
Bastida, Adolfo [1 ]
Zuniga, Jose [1 ]
Requena, Alberto [1 ]
Miguel, Beatriz [2 ]
机构
[1] Univ Murcia, Dept Quim Fis, E-30100 Murcia, Spain
[2] Univ Politecn Cartagena, Dept Ingn Quim & Ambiental, Cartagena 30203, Spain
关键词
excited states; ground states; intermolecular mechanics; liquid theory; rotational-vibrational energy transfer; vibrational modes; water; SELF-CONSISTENT-FIELD; QUANTUM-CLASSICAL DYNAMICS; HYDROGEN-BOND DYNAMICS; ENERGY RELAXATION; INFRARED-SPECTROSCOPY; MOLECULAR-DYNAMICS; TEMPERATURE-DEPENDENCE; NEUTRON SCATTERING; CONDENSED-PHASE; STOKES SHIFT;
D O I
10.1063/1.3266834
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The Ehrenfest method with quantum corrections is used to describe the vibrational relaxation of the bend fundamental in liquid water. All the vibrational degrees of freedom of the water molecules are described using quantum mechanics, while the remaining translational and rotational degrees of freedom are described classically. The relaxation time obtained compares well with experiment and with relaxation times calculated using other theoretical approximations. The presence of resonant intermolecular vibrational energy (VV) transfer is established with a maximum percentage of excited molecules, different from the initial one, of 9.2%. It is found through an effective kinetic fit that two VV transfers occur before relaxation of water to the vibrational ground state.
引用
收藏
页数:10
相关论文
共 85 条
[1]  
Allen M. P., 1987, Computer Simulation of Liquids, DOI [10.1093/oso/9780198803195.001.0001, DOI 10.1093/OSO/9780198803195.001.0001]
[2]   Vibrational couplings and ultrafast relaxation of the O-H bending mode in liquid H2O [J].
Ashihara, S. ;
Huse, N. ;
Espagne, A. ;
Nibbering, E. T. J. ;
Elsaesser, T. .
CHEMICAL PHYSICS LETTERS, 2006, 424 (1-3) :66-70
[3]   Ultrafast structural dynamics of water induced by dissipation of vibrational energy [J].
Ashihara, Satoshi ;
Huse, Nils ;
Espagne, Agathe ;
Nibbering, Erik T. J. ;
Elsaesser, Thomas .
JOURNAL OF PHYSICAL CHEMISTRY A, 2007, 111 (05) :743-746
[4]   IR and Raman spectra of liquid water: Theory and interpretation [J].
Auer, B. M. ;
Skinner, J. L. .
JOURNAL OF CHEMICAL PHYSICS, 2008, 128 (22)
[5]   Dynamical effects in line shapes for coupled chromophores: Time-averaging approximation [J].
Auer, B. M. ;
Skinner, J. L. .
JOURNAL OF CHEMICAL PHYSICS, 2007, 127 (10)
[6]   Strong feedback effect in the vibrational relaxation of liquid water [J].
Bakker, HJ ;
Lock, AJ ;
Madsen, D .
CHEMICAL PHYSICS LETTERS, 2004, 384 (4-6) :236-241
[7]   Delocalization of protons in liquid water [J].
Bakker, HJ ;
Nienhuys, HK .
SCIENCE, 2002, 297 (5581) :587-590
[8]   A modified Ehrenfest method that achieves Boltzmann quantum state populations [J].
Bastida, A ;
Cruz, C ;
Zúñiga, J ;
Requena, A ;
Miguel, B .
CHEMICAL PHYSICS LETTERS, 2006, 417 (1-3) :53-57
[9]   Surface hopping simulation of the vibrational relaxation of I2 in liquid xenon using the collective probabilities algorithm [J].
Bastida, A ;
Cruz, C ;
Zúñiga, J ;
Requena, A ;
Miguel, B .
JOURNAL OF CHEMICAL PHYSICS, 2004, 121 (21) :10611-10622
[10]   The Ehrenfest method with quantum corrections to simulate the relaxation of molecules in solution:: Equilibrium and dynamics [J].
Bastida, Adolfo ;
Cruz, Carlos ;
Zuniga, Jose ;
Requena, Alberto ;
Miguel, Beatriz .
JOURNAL OF CHEMICAL PHYSICS, 2007, 126 (01)