J. Phys. Chem. B 2003, 107, 229-236
229
Photodissociation and Vibrational Relaxation of OClO at Liquid Surfaces Ilya Chorny, John Vieceli, and Ilan Benjamin* Department of Chemistry, UniVersity of California, Santa Cruz, California 95064 ReceiVed: August 1, 2002; In Final Form: October 21, 2002
The photodissociation dynamics of OClO to O + ClO on the 2A2 excited state and the vibrational relaxation of OClO in the ground electronic state at the interface of several polar liquids are studied using classical molecular dynamics computer simulations. The results are compared with recent calculations and experiments of photodissociation and vibrational relaxation of OClO in bulk water, acetonitrile, and ethanol. In contrast with substantial geminate recombination in the bulk, the photodissociation at the liquid/vapor interface of all three liquids gives rise to nearly 100% cage escape. In most of the trajectories at least one of the dissociation fragments desorb, although a significant percentage of the ClO fragments remain adsorbed at the interface. The reduced density at the interface gives rise to reduced friction and to slower vibrational relaxation of ground-state OClO (which may form as a result of geminate recombination of the photofragments). The vibrational relaxation of ground-state OClO is slower at the interface than in the bulk by a factor of 2-4, depending on the solvent and the excitation energy.
I. Introduction The photodissociation of OClO to give (a) OCl + O, or (b) Cl + O2, has been extensively studied in the gas phase1-5 and in bulk liquids6-21 due to its possible environmental impact.22 These studies have contributed to the basic understanding of the nature of the excited-state potentials and the specific solvent-solute interactions that give rise to the observed quantum yield of the different photoproducts and the vibrational relaxation rate of the recombined OClO. These studies show that the O and ClO photofragments geminately recombine in water in less than 1 ps to give a ground-state OClO with a quantum yield of about 0.8. The geminate recombination yield is reduced by a factor of 6 when the photodissociation takes place in acetonitrile17 and by almost a factor of 2 in ethanol.20 The OClO formed undergoes vibrational relaxation that is approximately three time faster in water than in acetonitrile and ethanol. While the experimental and theoretical studies have helped gain valuable insight into the bulk phase photochemistry of OClO, we lack basic knowledge about the photochemistry of OClO in other environments. A number of initial attempts to experimentally study this process at heterogeneous surfaces have been reported23,24 with the goal of furthering our understanding of the factors that can influence the yield of different photoproducts. Study of this reaction at liquid interfaces is important for the above reason and to provide additional insight and a molecularly based understanding into the effect of different solvent properties on the observed geminate recombination yield and vibrational relaxation rate. In addition, a number of important photochemical reactions in the atmosphere are believed to occur at the surface of amorphous ice particles or at the surface of liquid droplets. We have recently begun a systematic study of photodissociation and vibrational relaxation at liquid surfaces.25-27 These studies focused on vibrational relaxation of polar and nonpolar diatomic solutes in water26 and the photodissociation25 and * Corresponding author.
vibrational relaxation27 of a nonpolar tri-atomic solute (ICN) in a nonpolar solvent (chloroform). Examining OClO at the surface of polar protic and aprotic solvents is an important extension of the above studies. In two previous papers we reported our calculations on the vibrational relaxation28 and photodissociation29 of OClO in water, acetonitrile, and ethanol with results that are in good agreement with experiments. In this paper we discuss similar calculations carried out at the surface of these liquids with the goal of elucidating the role of the liquid interface region on vibrational relaxation and photodissociation of a polar molecule in polar solvents. While the calculations in the bulk show significant probability for geminate recombination (in reasonable agreement with experiments), the photodissociation at the liquid/vapor interface of all three liquids gives rise to nearly 100% cage escape. We show that this is consistent with much slower vibrational relaxation at the interface, which minimizes the probability of the OClO to be trapped in the excited state. We also observe significant desorption of the oxygen and, to a lesser degree, the ClO photofragments. The vibrational relaxation of ground state OClO is strongly energy dependent and slower at the interface than in the bulk by a factor of 2-4, depending on the solvent and the excitation energy. The rest of the paper includes in Section II a summary of the systems studied, the potential energy functions and the methods used to study the photodissociation and the vibrational relaxation. In Section III we discuss the results, followed by conclusions in Section IV. II. Systems and Methods In this section we discuss the potential energy functions and the methodology for conducting the photodissociation and the vibrational relaxation calculations at the liquid surface region. Each of the systems studied includes a single OClO molecule adsorbed at the liquid/vapor interface of one of the three solvents at 298 K. The shape of the simulation box is a parallelepiped whose size depends on the particular system and is listed in
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230 J. Phys. Chem. B, Vol. 107, No. 1, 2003
Chorny et al.
TABLE 1: The Systems Studied 3
the liquid
number of molecules
box dimensions (Å )
water acetonitrile ethanol
1024 500 500
31.3 × 31.3 × 100 35.1 × 35.1 × 100 36.5 × 36.5 × 100
Table 1. Three-dimensional periodic boundary conditions give rise to two liquid/vapor interfaces that are perpendicular to the long axis of the box (taken to be the Z direction). While OClO is a surface active molecule and tends to remain adsorbed at the interface, during a long simulation run it may diffuse to the bulk. For some of the molecular dynamics calculations, we employ a window potential, which prevents the molecule from escaping a 3 Å wide region centered at the Gibbs surface (the plane where the solvent density is 50% of the bulk value). This is simply done in order to increase the efficiency of data collection from the interface. Since the solute molecule does not interact with this potential when it is inside the window, this window potential does not affect any equilibrium calculations done at the interface. (The density profile of each of the three solvents and the probability distribution of the OClO center of mass will be discussed below.) A. Potential Energy Functions. We briefly describe here the potential energy functions used in this work. For a more detailed description the reader should consult the previous papers devoted to the study of OClO in the bulk liquids.28,29 1. OClO Ground- and Excited-State Potentials. The ground X 2B1 and the 2A2 excited electronic states of OClO are given by a three-dimensional modified LEPS form which is fitted to ab inito multireference configuration interaction calculations by K. A. Peterson30 in the Franck-Condon region. The groundstate dissociation energy of OClO (D0 ) 59 kcal/mol), data from photofragment translational energy spectroscopy experiments,3 and information about the potential energy functions of O2 31 and ClO32,33 are used as constraints in the fit. The potential is given explicitly by
UOClO(r1,r2,r3) ) ULEPS(r1,r2,r3) + ke-R(r1+r2)(r3 - r′3) + k1e-β[(r1-a) +(r2-a) ] 2
2
ULEPS(r1,r2,r3) ) Q1 + Q2 + Q3 - [0.5(J223 + J213 + J212)]1/2 Qi ) 0.5D1i[(e-β1i(ri-r1i) - 1)2 - 1] + 0.5D3i[(e-β3i(ri-r3i) + 1)2 - 1] Jij ) Ji - Jj i,j ) 1,2,3 i * j Ji ) 0.5D1i[(e-β1i(ri-r1i) - 1)2 - 1] - 0.5D3i[(e-β3i(ri-r3i) + 1)2 - 1] (1) where r1 and r2 are the two O-Cl bond lengths, r3 is the O-O distance, and r′3 is the O-O distance at the equilibrium OClO
bend angle (r′3 ) xr12+r22-2r1r2cosθeq). More details about these potentials including plots showing the quality of the fit to the ab inito data and the value of all the parameters for the ground- and excited-state potentials can be found elsewhere.29 An important feature of the excited-state potential is the existence of a late barrier to dissociation along the asymmetric stretch of OClO. This barrier is around 12 kcal/mol near the equilibrium OClO bond lengths, in agreement with estimates based on photofragment translational spectroscopy experiments.3
2. Liquids’ Potential Energy Functions. The liquid potentials used in this work have been shown to give reasonable structural, thermodynamic, and dynamic properties of bulk water,34 bulk liquid acetonitrile,35 and bulk ethanol.36 These potentials include an intramolecular part (which is necessary when studying photodissociation and vibrational relaxation processes in liquid) and an intermolecular part. The liquid intramolecular potential energy function for water is the spectroscopic potential of Kuchitso and Morino.37 The intramolecular potential for CH3CN is modeled using a harmonic force field for the CC and CN stretches and the CCN bend whose parameters are selected to reproduce the fundamental vibrational frequencies of gasphase CH3CN.38 For ethanol, the intramolecular potential energy function includes harmonic bond stretches, harmonic angle bends, and a three-term Fourier series for the CCOH torsional mode. The CH3 and CH2 groups in ethanol and the CH3 group in acetonitrile are treated as united atoms with the appropriate mass of these groups. The intermolecular part of the potential is modeled as a pairwise sum of Lennard-Jones + Coulomb terms:
U(r) )
4ij ∑ i
