Spin-orbit coupling in O2(v)+O2 collisions: a new energy transfer mechanism

A reduced dimensionality model is used to study the relaxation of highly vibrationally excited O(2)(X (3)Sigma(g) (-),v>/=20) in collisions with O(2)(X (3)Sigma(g) (-),v=0). Spin-orbit coupled potential energy surfaces are employed to incorporate the vibrational-to-electronic energy transfer mechanism involving the O(2)(a (1)Delta(g)) and O(2)(b (1)Sigma(g) (+)) excited states. The transition probabilities obtained show a sharp increase for v>/=26 providing the first direct evidence of the important role played by the electronic energy transfer processes in the depletion of O(2)(X (3)Sigma(g) (-),v>/=26).     

Spin-orbit coupling in O2(upsilon)+O2 collisions: I. Electronic structure calculations on dimer states involving the X 3Sigmag-, a 1Deltag, and b 1Sigmag+ states of O2

The importance of vibrational-to-electronic (V-E) energy transfer mediated by spin-orbit coupling in the collisional removal of O2(X 3Sigmag-,upsilon>or=26) by O2 has been reported in a recent communication [F. Dayou, J. Campos-Martinez, M. I. Hernandez, and R. Hernandez-Lamoneda, J. Chem. Phys. 120, 10355 (2004)]. The present work provides details on the electronic properties of the dimer (O2)2 relevant to the self-relaxation of O2(X 3Sigmag-,upsilon>0) where V-E energy transfer involving the O2(a 1Deltag) and O2(b 1Sigmag+) states is incorporated. Two-dimensional electronic structure calculations based on highly correlated ab initio methods have been carried out for the potential-energy and spin-orbit coupling surfaces associated with the ground singlet and two low-lying excited triplet states of the dimer dissociating into O2(X 3Sigmag-)+O2(X 3Sigmag-), O2(a 1Deltag)+O2(X 3Sigmag-), and O2(b 1Sigmag+)+O2(X 3Sigmag-). The resulting interaction potentials for the two excited triplet states display very similar features along the intermolecular separation, whereas differences arise with the ground singlet state for which the spin-exchange interaction produces a shorter equilibrium distance and higher binding energy. The vibrational dependence is qualitatively similar for the three studied interaction potentials. The spin-orbit coupling between the ground and second excited states is already nonzero in the O2+O2 dissociation limit and keeps its asymptotic value up to relatively short intermolecular separations, where the coupling increases for intramolecular distances close to the equilibrium of the isolated diatom. On the other hand, state mixing between the two excited triplet states leads to a noticeable collision-induced spin-orbit coupling between the ground and first excited states. The results are discussed in terms of specific features of the dimer electronic structure (including a simple four-electron model) and compared with existing theoretical and experimental data. This work gives theoretical insight into the origin of electronic energy-transfer mechanisms in O2+O2 collisions.     

Kinetic study of vibrational energy transfer from a wide range of vibrational levels of O2(X(3)Sigma(g)-, v = 6-12) to CF4

A wide range of vibrational levels of O2(X(3)Sigma(g)(-), v = 6-13) generated in the ultraviolet photolysis of O3 was selectively detected by the laser-induced fluorescence (LIF) technique. The time-resolved LIF-excited B(3)Sigma(u)(-)-X(3)Sigma(g)(-) system in the presence of CF4 has been recorded and analyzed by the integrated profiles method (IPM). The IPM permitted us to determine the rate coefficients k(v)(CF4) for vibrational relaxation of O2(X(3)Sigma(g)(-), v = 6-12) by collisions with CF4. Energy transfer from O2 (v = 6-12) to CF4 is surprisingly efficient compared to that of other polyatomic relaxation partners studied so far. The k(v)(CF4) increases with vibrational quantum number v from [1.5 +/- 0.2(2sigma)] x 10(-12) for v = 6 to [7.3 +/- 1.5(2sigma)] x 10(-11) for v = 12, indicating that the infrared-active nu3 vibrational mode of CF4 mainly governs the energy transfer with O2(X(3)Sigma(g)(-), v = 6-12). The correlation between the rate coefficients and fundamental infrared intensities has been discussed based on a comparison of the efficiency of energy transfer by several collision partners.     

Ab initio potential-energy surfaces of O2(X3Sigmag -, a1Deltag, b1Sigmag +) +O2 (X3Sigmag -, a1Deltag, b1Sigmag +): mechanism of quenching of O2 (a 1Deltag)

Ab initio computational studies were carried out in order to explore the possible mechanisms of quenching of O(2)(a (1)Delta(g)) by O(2)(X (3)Sigma(g) (-)): the self-quenching of O(2)(a (1)Delta(g)) and other energy-transfer processes involving two O(2) molecules. All eighteen states arising from two O(2) molecules in the X (3)Sigma(g) (-), a (1)Delta(g), and b (1)Sigma(g) (+) states are considered. After scans at the state-averaged complete active space self-consistent field method to identify possible regions of crossing between states belonging to different asymptotes, complete active state second-order perturbation theory high-symmetry optimization and low-symmetry scans established that four different minima on the seams of crossing (MSXs), arising between the a+a manifold and the X+b manifold and responsible for self-quenching: O(2)(a (1)Delta(g))+O(2)(a (1)Delta(g))-->O(2)(X (3)Sigma(g) (-))+O(2)(b (1)Sigma(g) (+)), have coplanar C(2h) or C(2v) symmetries and are only 0.45 eV barrier relative to the a+a asymptote and energetically easily accessible. The rate constant for this process was estimated based on the Landau-Zener formalism. The MSXs for quenching of O(2)(a (1)Delta(g)) by the ground state O(2)(X (3)Sigma(g) (-)):O(2)(a (1)Delta(g))+O(2)(X (3)Sigma(g) (-))-->O(2)(X (3)Sigma(g) (-))+O(2)(X (3)Sigma(g) (-)) require higher energies and the process is not likely to be important.     

Vibrational relaxation of O2(X3 Sigma g-, v = 9-13) by collisions with O2

Vibrationally excited O(2)(X(3) Sigmag(-)) was generated in the UV laser flash photolysis of O(3) and single vibrational level was detected via laser-induced fluorescence (LIF) in the B(3) Sigmau(-)-X(3) Sigmag(-) system. The time-resolved LIF of adjacent vibrational levels has been analyzed by the integrated-profiles method and the rate coefficients for single-quantum relaxation, O(2)(X(3)Sigmag(-), v = 9-13)+ O(2)(v = 0)--> O(2)(X(3)Sigmag(-), v - 1)+ O(2)(v = 1), have been determined. To the best of our knowledge, the rate coefficients for v = 12 and 13 are measured for the first time in the present study. The efficiency of relaxation is higher at lower vibrational levels, indicating that a small energy mismatch is suitable for the energy transfer. The vibrational level dependence of all the rate coefficients for the relaxation measured in the present study and previously reported by several groups can be rationalized by the energy gap law.     

Reaction dynamics of Si(3PJ)+O2-->SiO(X 1 Sigma+)+O studied by a crossed-beam laser-induced fluorescence technique

Oxidation reaction of the ground state Si atom was studied by using a crossed molecular beam technique at 13.0 kJ/mol of collision energy. The Si atomic beam was generated by laser vaporization and crossed with the oxygen molecular beam at right angle. Products at the crossing region were detected by the laser-induced fluorescence (LIF). The LIF of SiO(A 1 Pi-X 1 Sigma+) was used to determine the vibrational state distribution of the electronic ground state, SiO(X 1 Sigma+). The determined distribution was inverted with the maximum population at v"=4, and in good agreement with the recent quasiclassical trajectory calculation on the singlet potential energy surface. The agreement suggested that an abstraction mechanism is dominant at the collision energy studied here. One of the counterproducts, O(3PJ), was also observed by the vacuum ultraviolet LIF and the distribution of the spin-orbit levels were determined. The formation of O(3PJ) was consistent with the significant population of v"=7 and 8 states of SiO, which could be explained by the presence of the triplet product channel with higher exothermicity.     

Accurate ab initio intermolecular potential energy surface for the quintet state of the O2(3Sigma(g)-)-O2(3Sigma(g)-) dimer

A new potential energy surface (PES) for the quintet state of rigid O(2)((3)Sigma(g)(-)) + O(2)((3)Sigma(g)(-)) has been obtained using restricted coupled-cluster theory with singles, doubles, and perturbative triple excitations [RCCSD(T)]. A large number of relative orientations of the monomers (65) and intermolecular distances (17) have been considered. A spherical harmonic expansion of the interaction potential has been built from the ab initio data. It involves 29 terms, as a consequence of the large anisotropy of the interaction. The spherically averaged term agrees quite well with the one obtained from analysis of total integral cross sections. The absolute minimum of the PES corresponds to the crossed (D(2d)) structure (X shape) with an intermolecular distance of 6.224 bohrs and a well depth of 16.27 meV. Interestingly, the PES presents another (local) minimum close in energy (15.66 meV) at 6.50 bohrs and within a planar skewed geometry (S shape). We find that the origin of this second structure is due to the orientational dependence of the spin-exchange interactions which break the spin degeneracy and leads to three distinct intermolecular PESs with singlet, triplet, and quintet multiplicities. The lowest vibrational bound states of the O(2)-O(2) dimer have been obtained and it is found that they reflect the above mentioned topological features of the PES: The first allowed bound state for the (16)O isotope has an X structure but the next state is just 0.12 meV higher in energy and exhibits an S shape.     

Vibrational structure, spin-orbit splitting, and bond dissociation energy of Cl2+(X2 Pi g) studied by zero kinetic energy photoelectron spectroscopy and ion-pair formation imaging method

The isotopomer-resolved vibrational and spin-orbit energy structures of Cl(2) (+)(X (2)Pi(g)) have been studied by one-photon zero kinetic energy photoelectron spectroscopy. The spin-orbit energy splitting for the ground vibrational state is determined as 717.7+/-1.5 cm(-1), which greatly improves on the accuracy of the previously reported data. This value is found to be in good agreement with the ab initio quantum chemical calculation taking account of the inner shell electron correlation. The first adiabatic ionization energy (IE) of Cl(2) is determined as 92 645.9+/-1.0 cm(-1). Using the ion-pair formation imaging method to discriminate signals of Cl(+)((1)D(2)) from those of Cl(+)((3)P(j)), the threshold for ion-pair (E(tipp)) production, Cl(+)((1)D(2))+Cl(-)((1)S(0))<--Cl(2)(X (1)Sigma(g) (+)), is determined as 107 096(-2) (+8) cm(-1). By using the determined IE and E(tipp) for Cl(2) and also the reported IE and electronic affinity for chlorine atom, the bond dissociation energies of Cl(2)(X (1)Sigma(g) (+)) and Cl(2) (+)(X (2)Pi(g)) have been determined as 19 990(-2) (+8) and 31 935.1(-2) (+8), respectively.     

Photodissociation channels for N2O near 130 nm studied by product imaging

The photodissociation of N(2)O at wavelengths near 130 nm has been investigated by velocity-mapped product imaging. In all, five dissociation channels have been detected, leading to the following products: O((1)S)+N(2)(X (1)Sigma), N((2)D)+NO(X (2)Pi), N((2)P)+NO(X (2)Pi), O((3)P) + N(2)(A (3)Sigma(+) (u)), and O((3)P) + N(2)(B (3)Pi(g)). The most significant channel is to the products O((1)S) + N(2)(X(1)Sigma), with strong vibrational excitation in the N(2). The O((3)P) + N(2)(A,B):N((2)D,(2)P) + NO branching ratio is measured to be 1.4 +/- 0.5, while the N(2)(A) + O((3)P(J)):N(2)(B) + O((3)P(J)) branching ratio is determined to be 0.84+/-0.09. The spin-orbit distributions for the O((3)P(J)), N((2)P(J)), and N((2)D(J)) products were also determined. The angular distributions of the products are in qualitative agreement with excitation to the N(2)O(D (1)Sigma(+)) state, with participation as well by the (3)Pi(v) state.     

Measurement of the rate coefficient for collisional removal of O2(X3Sigma- g, upsilon=1) by O(3P)

We report a laboratory measurement of the rate coefficient for the collisional removal of O(2)(X(3)Sigma(g) (-),upsilon=1) by O((3)P) atoms. In the experiments, 266-nm laser light photodissociates ozone in a mixture of molecular oxygen and ozone. The photolysis step produces vibrationally excited O(2)(a(1)Delta(g)) that is rapidly converted to O(2)(X(3)Sigma(g) (-),upsilon=1-3) in a near-resonant electronic energy-transfer process with ground-state O(2). In parallel, a large amount of O((1)D) atoms is generated that promptly relaxes to O((3)P). Under the conditions of the experiments, only collisions with the photolytically produced O((3)P) atoms control the lifetime of O(2)(X(3)Sigma(g) (-),upsilon=1), because its removal by molecular oxygen at room temperature is extremely slow. Tunable 193-nm laser light monitors the temporal evolution of the O(2)(X(3)Sigma(g) (-),upsilon=1) population by detection of laser-induced fluorescence near 360 nm. The removal rate coefficient for O(2)(X(3)Sigma(g) (-),upsilon=1) by O((3)P) atoms is (3.2+/-1.0)x10(-12) cm(3) s(-1) (2sigma) at a temperature of 315+/-15 K (2sigma). This result is essential for the analysis and correct interpretation of the 6.3-mum H(2)O(nu(2)) band emission in the Earth's mesosphere and indicates that the deactivation of O(2)(X (3)Sigma(g) (-),upsilon=1) by O((3)P) atoms is significantly faster than the nominal values recently used in atmospheric models.     

Observation and calculation of the Cs2 2 3Delta(1g) and b 3Pi(0u) states

The Cs(2) 2 (3)Delta(1g) and b (3)Pi(0u) states have been observed by infrared-infrared double resonance spectroscopy for the first time. 221 2 (3)Delta(1g)<--A (1)Sigma(u) (+)<--X (1)Sigma(g) (+) double resonance lines have been assigned to transitions into the 2 (3)Delta(1g) v=6-13 vibrational levels. Resolved fluorescence into the b (3)Pi(0u) v(')=0-48 levels has been recorded. Molecular constants and potential energy curves are determined by the global fit of the entire set of the experimental data. Theoretical potential energy curves of the 2 (3)Delta(g) and b (3)Pi(u) states have been determined in the framework of the pseudopotential method and are compared with the experimental results.     

Study on the photodissociation spectra of CS2+ via B2Sigma u+ and C2Sigma g+ electronic states

The photodissociation spectra of CS(2)(+) ions via B(2)Sigma(u)(+) and C(2)Sigma(g)(+) electronic states have been studied by using two-photon excitation, where the parent CS(2)(+) ions were prepared by [3 + 1] REMPI (resonance-enhanced multiphoton ionization) at 483.2 nm from the jet-cooled CS(2) molecules. The [1 + 1] photodissociation spectrum of CS(2)(+) via the B(2)Sigma(u)(+)(upsilon(1)upsilon(2)0) <-- X(2)Pi(g,3/2)(000) transition was obtained by scanning the dissociation laser in the wavelength range of 270-285 nm and detecting the signal of both S(+) and CS(+). The [1 + 1'] photodissociation spectra of CS(2)(+) were obtained by fixing the first dissociation laser at 281.94 or 277.15 nm to excite the B(2)Sigma(u)(+) (000 or 100) <-- X(2)Pi(g,3/2)(000) transitions and scanning the second dissociation laser in the range of 606-763 nm to excite C(2)Sigma(g)(+)(upsilon(1)upsilon(2)0) <-- B(2)Sigma(u)(+)(000,100) transitions. New spectroscopic constants of nu(1) = 666.2 +/- 2.5 cm(-1), nu(2) = 363.2 +/- 1.9 cm(-1), chi(11) = -5.5 +/- 0.1 cm(-1), chi(22) = 1.6 +/- 0.1 cm(-1), chi(12) = -8.6 +/- 0.2 cm(-1), and k(122) = 44.9 +/- 2.5 cm(-1) (Fermi resonance constant) for the C(2)Sigma(g)(+) state are deduced from the [1 + 1'] photodissociation spectra. On the basis of the [1 + 1] and [1 + 1'] photodissociation spectra, the wavelength and level dependence of the product branching ratios CS(+)/S(+) has been found and the dissociation dynamics of CS(2)(+) ions via B(2)Sigma(u)(+) and C(2)Sigma(g)(+) electronic states are discussed.     

Renner-Teller effect in C2H2+(X2Pi u) studied by rotationally resolved zero kinetic energy photoelectron spectroscopy

The Renner-Teller effect in C(2)H(2)(+)(X(2)Pi(u)) has been studied by using zero kinetic energy (ZEKE) photoelectron spectroscopy and coherent extreme ultraviolet (XUV) radiation. The rotationally resolved vibronic spectra have been recorded for energies up to 2000 cm(-1) above the ground vibrational state. The C triple bond C symmetric stretching (upsilon(2)), the CCH trans bending (upsilon(4)), and the CCH cis bending (upsilon(5)) vibrational excitations have been observed. The assigned vibronic bands are 4(1)(1)(kappa(2)Sigma(u)(+))(hot band), 4(1)(0)(mu/kappa(2)Sigma (u)(-/+)), 5(1)(0)(mu/kappa(2)Sigma (g)(+/-)), and 4(2)(0)(mu(2)Pi(u)), 4(2)(0)(kappa(2)Pi(u)), 4(1)(0)5(1)(0) (mu(2)Pi(g)), 0(0)(0)(X(2)Pi(u)), and 2(1)(0)(X(2)Pi(u)). The Renner-Teller parameters, the harmonic frequencies, the spin-orbit coupling constants, and the rotational constants for the corresponding vibronic bands have been determined by fitting the spectra with energy eigenvalues from the Hamiltonian that considers simultaneously Renner-Teller coupling, vibrational energies, rotational energies, and spin-orbit coupling interaction.     

A reliable ab initio potential energy surface and vibrational states for the ground electronic state of HgH2(X1Sigma+g)

A three-dimensional global potential energy surface for the ground (X (1)Sigma(+)(g))electronic state of HgH(2) is constructed from more than 13,00 ab initio points. These points are generated using an internally contracted multireference configuration interaction method with the Davidson correction and a large basis set. Low-lying vibrational energy levels of HgH(2), HHgD, and HgD(2) calculated using the Lanczos algorithm are found to be in good agreement with the available experimental band origins. The majority of the vibrational energy levels up to 9000 cm(-1) are assigned with normal mode quantum numbers. Our results indicate a gradual transition for the stretching vibrations from the normal mode regime at low energies to the local mode regime near 9000 and 8000 cm(-1) for HgH(2) and HgD(2), respectively, as evidenced by a decreasing energy gap between the (0,0,n(3)) and (1,0,n(3)-1) vibrational states and bifurcation of the corresponding wave functions.     

The potential energy curve of the ground state of the potassium dimer, X1Sigma(g)+ K2

The most recently published listings of vibrational term values and corresponding turning points of the potential energy curve of X (1)Sigma(g) (+) K(2) consist of two sets of data: energy levels v(")=0-73 and v(")=74-81. The two sets of data are found to exhibit a discontinuity. This is due to different Dunham coefficients used to produce a listing of turning points for levels v(")=0-73 and for levels v(")=74-81. This work provides an explicit, self-consistent listing of turning points for the entire domain of observed vibrational term values. New values are reported for levels v(")=53-81. This potential yields eigenvalues in excellent agreement with experimental vibrational term values and predicts two more bound levels. A "universal" function proposed in 1991 for predicting potential energy curves yields eigenvalues for levels v(")=0-81 (99.96% of dissociation) that have an average absolute deviation from the experiment of 0.95 cm(-1).     

Theoretical determination of rate constants for vibrational relaxation and reaction of OH(X 2Pi, v = 1) with O(3P) atoms

Collisions of the vibrationally excited OH(v = 1) molecule with atomic oxygen are investigated theoretically using a coupled-states, statistical capture (CS-ST) model. Vibrational relaxation can occur by inelastic scattering, and the vibrationally excited molecule can also be removed by reaction to form O(2) in both the ground (X (3)Sigma(g)(-)) and first excited (a (1)Delta(g)) state. In the former case, reaction occurs on the lowest potential energy surface of (2)A(") symmetry, and, in the latter case, by reaction on the lowest potential energy surface of (2)A(') symmetry. We report new ab initio potential energy surfaces for both these states in the product and reactant regions necessary for application of the coupled-states, statistical method. Comparison with exact, reactive scattering calculations within the J-shifting approximation indicate that the CS-ST rate constants for removal of OH(v = 1) can be expected to be reasonably accurate. Our calculated rate constants at 300 K agree well with the experimental results of Khachatrian and Dagdigian [Chem. Phys. Lett. 415, 1 (2005)]. Reaction to yield O(2) (X (3)Sigma(g)(-)) is the dominant removal pathway. At subthermal temperatures, the rate constants for the various vibrational quenching processes all increase down to T approximately = 60 K and then decrease at lower temperature.     

Reaction dynamics of Y + O2--> YO(X,A',A)+ O(3P(J)) studied by the crossed-beam technique

The dynamics of the reaction, Y + O2--> YO + O was studied by using the crossed-beam technique at several collision energies from 10.3 to 52.0 kJ mol(-1). The Y atomic beam was generated by laser vaporization and crossed with the O2 beam at a right angle. Among the energetically accessible electronic states of YO, the formation of the A2Pi and A'2Delta states was observed by their chemiluminescence at all collision energies. By analyzing the chemiluminescence spectra of YO(A2Pi(1/2,3/2)-X2Sigma+), vibrational state distributions and relative populations of spin-orbit states were determined for YO(A2Pi(1/2,3/2)). At low collision energies, the vibrational distributions agree quite well with those expected from the statistical energy partitioning, while a little deviation from the statistical expectation was observed at the highest energy, 52.0 kJ mol(-1). The populations of two spin-orbit states are in good agreement with the statistical expectations at all collision energies. The vacuum ultraviolet laser-induced fluorescence (VUV-LIF) technique was employed to determine the distributions of spin-orbit states of the product O(3P(J)) at two collision energies, 20.7 and 52.0 kJ mol(-1). The line shapes of the O atom transitions were analyzed to determine relative branching ratio of the ground state to the excited states of YO, i.e. YO(X2Sigma+)+ O(3P(J))vs. YO(A2Pi and A'2Delta)+ O(3P(J)). The results showed that the electronically excited YO was formed with comparable amount with the ground state which is statistically more favorable, and suggested the occurrence of two mechanisms taking place in the title reaction.     

Gallium oxide and dioxide: investigation of the ground and low-lying electronic states via anion photoelectron spectroscopy

The GaO and GaO2 molecules were investigated using negative ion photoelectron spectroscopy. All the photoelectron spectra showed vibrationally resolved progressions. With the aid of electronic structure calculations and Franck-Condon spectral simulations, different molecular parameters and energetics of GaO-/GaO and GaO2-/GaO2 were determined, including the electron affinity of GaO, the vibrational frequency of GaO-, and the term energy, spin-orbit splitting, and vibrational frequency for the first excited A 2PiOmega state of GaO. The GaO2- photoelectron spectra comprised three bands assigned as transitions from the linear X 1Sigma(g)+ ground state of GaO2- to three linear neutral states: the A 2Pi(g), B 2Pi(u), and C 2Sigma(u) + states. The symmetric stretch frequencies of the anion and three neutral states as well as the spin-orbit splitting of the neutral 2Pi states were determined. Electronic structure calculations found the neutral lowest energy linear structure to be only 63 meV higher than the neutral bent geometry.