A velocity map imaging study of the one and two photon dissociations of state-selected DCl+ cations

DCl(+)(X (2)Pi(32),v(+")=0) cations have been prepared by 2+1 resonance enhanced multiphoton ionization, and their subsequent fragmentation following excitation at numerous wavelengths in the range of 240-350 nm studied by velocity map imaging of the resulting Cl(+) products. This range of excitation wavelengths allows selective population of A (2)Sigma(+) state levels with all vibrational (v(+')) quantum numbers in the range 0< or =v(+')< or =15. Image analysis yields wavelength dependent branching ratios and recoil anisotropies of the various D+Cl(+) ((3)P(J), (1)D, and (1)S) product channels. Levels with 10< or =v(+')< or =15 have sufficient energy to predissociate, forming D+Cl(+)((3)P(J)) products with perpendicular recoil anisotropies-consistent with the A (2)Sigma(+)<--X (2)Pi parent excitation and subsequent fragmentation on a time scale that is fast compared with the parent rotational period. Branching into the various spin-orbit states of the Cl(+)((3)P(J)) product is found to depend sensitively upon v(+') and, in the case of the v(+')=13 level, to vary with the precise choice of excitation wavelength within the A (2)Sigma(+)<--X (2)Pi(13,0) band. Such variations have been rationalized qualitatively in terms of the differing contributions made to the overall predissociation rate of DCl(+)(A,v(+')) molecules by coupling to repulsive states of (4)Pi, (4)Sigma(-), and (2)Sigma(-) symmetries, all of which are calculated to cross the outer limb of the A (2)Sigma(+) state potential at energies close to that of the v(+')=10 level. Cl(+)((3)P(J)) fragments are detected weakly following excitation to A (2)Sigma(+) state levels with v(+')=0 or 1, Cl(+)((1)D) fragments dominate the ion yield when exciting via 2< or =v(+')< or =6 and via v(+')=9, while Cl(+)((1)S) fragments dominate the Cl(+) images obtained when exciting via levels with v(+')=7 and 8. Analysis of wavelength resolved action spectra for forming these Cl(+) ions and of the resulting Cl(+) ion images shows that (i) these ions all arise via two photon absorption processes, resonance enhanced at the one photon energy by the various A(v(+')<10) levels, (ii) the first A (2)Sigma(+)<--X (2)Pi absorption step is saturated under the conditions required to observe significant two photon dissociation, and (iii) the final absorption step from the resonance enhancing A(v(+')) level involves a parallel transition.     

Electronically excited-state properties and predissociation mechanisms of phosphorus monofluoride: a theoretical study including spin-orbit coupling

The 51 Ω states generated from the 22 Λ - S states of phosphors monofluoride have been investigated using the valence internally contracted multireference configuration interaction method with the Davidson correction and the entirely uncontracted aug-cc-pV5Z basis set. The spin-orbit coupling is computed using the state interaction approach with the Breit-Pauli Hamiltonian. Based on the calculated potential energy curves, the spectroscopic constants of the bound and quasibound Λ - S and Ω states are obtained, and very good agreement with experiment is achieved. Several quasibound states caused by avoided crossings are found. Various curve crossings and avoided crossings are revealed, and with the help of our computed spin-orbit coupling matrix elements, the predissociation mechanisms of the a(1)Δ, b(1)Σ(+), e(3)Π, g(1)Π, and (3)(3)Π states are analyzed. The intricate couplings among different electronic states are investigated. We propose that the avoided crossing between the A(3)Π(0 +) and b(1)Σ(0+) (+) states may be responsible for the fact that the A(3)Π ν' ≥ 12 vibrational levels can not be observed in experiment. The transition properties of the A(3)Π - X(3)Σ(-) transition are studied, and our computed Franck-Condon factors and radiative lifetimes match the experimental results very well.     

Extensive theoretical study on the low-lying electronic states of silicon monofluoride cation including spin-orbit coupling

Ab initio calculations on the low-lying electronic states of SiF+ are performed using the internally contracted multireference configuration interaction method with the Davidson correction and entirely uncontracted aug-cc-pV5Z basis set. The effects of spin-orbit coupling are accounted for by the state interaction approach with the full Breit-Pauli Hamiltonian. The entire 23 Omega states generated from the 12 valence Lambda-S states, which correlate with the first dissociation channel are studied for the first time. Good agreement is found between the calculated results and the available experimental data. The spin-orbit coupling effects on the potential energy curves and spectroscopic properties are studied. Various curve crossings are revealed, which could lead to the predissociation of the a3Pi, A1Pi, and (2)3Sigma+ states and the predissociation pathways are analyzed based upon the calculated spin-orbit matrix elements. The calculated ionization potentials of the ground-state SiF to a few states of SiF+ are in good agreement with the available experimental measurements. Moreover, the transition dipole moments of the dipole-allowed transitions and the transition properties for the A3Pi0+ -X1Sigma+ 0+ and B3Pi1-X1Sigma+ 0+ transitions are predicted, including the Franck-Condon factors and the radiative lifetimes.     

Resonant coupling of bound excitons with LO phonons in ZnO: excitonic polaron states and Fano interference

We report on a photoluminescence observation of robust excitonic polarons due to resonant coupling of exciton and longitudinal optical (LO) phonon as well as Fano-type interference in high quality ZnO crystal. At low enough temperatures, resonant coupling of excitons and LO phonons leads to not only traditional Stokes lines (SLs) but also up to second-order anti-Stokes lines (ASLs) besides the zero-phonon line (ZPL). The SLs and ASLs are found to be not mirror symmetric with respect to the ZPL, strongly suggesting that they are from different coupling states of exciton and phonons. Besides these spectral features showing the quasiparticle properties of exciton-phonon coupling system, the first-order SL is found to exhibit characteristic Fano lineshape, caused by quantum interference between the LO components of excitonic polarons and the continuous phonon bath. These findings lead to a new insight into fundamental effects of exciton-phonon interactions.     

1 Pi<--X1 Sigma+ band systems of jet-cooled ScCo and YCo

Rotationally resolved resonant two-photon ionization (R2PI) spectra of ScCo and YCo are reported. The measured spectra reveal that these molecules possess ground electronic states of (1)Sigma(+) symmetry, as previously found in the isoelectronic Cr(2) and CrMo molecules. The ground state rotational constants for ScCo and YCo are B(0)(")=0.201 31(22) cm(-1) and B(0) (")=0.120 96(10) cm(-1), corresponding to ground state bond lengths of r(0) (")=1.812 1(10) A and r(0) (")=1.983 0(8) A, respectively. A single electronic band system, assigned as a (1)Pi<--X (1)Sigma(+) transition, has been identified in both molecules. In ScCo, the (1)Pi state is characterized by T(0)=15,428.8, omega(e)(')=246.7, and omega(e)(')x(e)(')=0.73 cm(-1). In YCo, the (1)Pi state has T(0)=13 951.3, omega(e)(')=231.3, and omega(e)(')x(e) (')=2.27 cm(-1). For YCo, hot bands originating from levels up to v(")=3 are observed, allowing the ground state vibrational constants omega(e)(")=369.8, omega(e)(")x(e)(")=1.47, and Delta G(12)(")=365.7 cm(-1) to be deduced. The bond energy of ScCo has been measured as 2.45 eV from the onset of predissociation in a congested vibronic spectrum. A comparison of the chemical bonding in these molecules to related molecules is presented.     

Extensive theoretical study on electronically excited states and predissociation mechanisms of sulfur monoxide including spin-orbit coupling

The potential energy curves of the 69 Ω states generated from the 24 Λ-S states of sulfur monoxide are calculated for the first time using the internally contracted multireference configuration interaction method with the Davidson correction and the entirely uncontracted aug-cc-pV5Z basis set. Spin-orbit coupling is taken into account by the state interaction approach with the full Breit-Pauli Hamiltonian. Very good agreement is achieved between our computed spectroscopic properties and the available experimental data. The transition properties of the B(3)Σ(-) -X(3)Σ(-) and (4)1-X0(+) transitions are predicted, and our computed Franck-Condon factors and radiative lifetimes match the experimental results very well. The predissociation mechanisms are investigated, and various new predissociation channels are located. We present a new interpretation on the breaking-off of the rotational levels of the B(3)Σ(-) lower vibrational states observed in experiment, and propose that the predissociation is induced by the Coriolis coupling between the B(3)Σ(-) rovibrational levels and the A(3)Π state. Our calculations indicate that, at ν' = 9, the B(3)Σ(-) state predissociates via the C(3)Π state; around ν' = 14, three spin-orbit-induced predissociation pathways via (1)(5)Σ(+) , (2)(5)Π, and e(1)Π would be open; around ν' = 17, the pathways via (2)(1)Σ(+) , (2)(3)Σ(+) and (2)(5)Σ(+) would contribute. These satisfactorily explain the experimental results about the diffuseness of the B(3)Σ(-) bands. Furthermore, various predissociation pathways of the C'(3)Π state are predicted, through which the C'(3)Π state could predissociate rapidly.     

Experimental and theoretical studies of the CN-Ar van der Waals complex

The CN-Ar van der Waals complex has been observed using the B (2)Sigma(+)-X (2)Sigma(+) and A (2)Pi-X (2)Sigma(+) electronic transitions. The spectra yield a dissociation energy of D(0")=102+/-2 cm(-1) and a zero-point rotational constant of B(0")=0.067+/-0.005 cm(-1) for CN(X)-Ar. The dissociation energy for CN(A)-Ar was found to be D(0')=125+/-2 cm(-1). Transitions to vibrationally excited levels of CN(B)-Ar dominated the B-X spectrum, indicative of substantial differences in the intermolecular potential energy surfaces (PESs) for the X and B states. Ab initio PESs were calculated for the X and B states. These were used to predict rovibrational energy levels and van der Waals bond energies (D(0")=115 and D(0')=183 cm(-1)). The results for the X state were in reasonably good agreement with the experimental data. Spectral simulations based on the ab initio potentials yielded qualitative insights concerning the B-X spectrum, but the level of agreement was not sufficient to permit vibronic assignment. Electronic predissociation was observed for both CN(A)-Ar and CN(B)-Ar. The process leading to the production of CN(A,nu=8,9) fragments from the predissociation of CN(B,nu=0)-Ar was characterized using time-resolved fluorescence and optical-optical double resonance measurements.     

Electronic excited-state mixing in NeCl2

Ab initio calculations that explicitly include spin-orbit interactions are reported for the NeCl2 system of electronic states. A surprising curve crossing is observed for the C2v, T-shaped geometry. Away from the C2v geometry, the states mix, as expected. On the basis of these new results we propose a new mechanism for electronic energy transfer from highly vibrationally excited levels of the B electronic state of the chlorine molecule. It is proposed that as long as vibrational predissociation of NeCl2 proceeds by direct coupling of the initial state to the continuum states the Ne atom does not sample geometries that efficiently quench the Cl2 B electronic state. However, when the vibrational dynamics changes to the intramolecular vibrational relaxation regime the Ne atom becomes quite effective at coupling the Cl2 B3Pi0u+ state with a 3Pi2g state.     

Low-lying electronic states and Cl-loss photodissociation of the C2H3Cl+ ion studied using multiconfiguration second-order perturbation theory

We studied the 1(2)A' '(X2A' '), 1(2)A' (A2A'), 2(2)A' ' (B2A' '), and 2(2)A' (C2A') states of the C2H3Cl+ ion using the complete active space self-consistent field (CASSCF) and multiconfiguration second-order perturbation theory (CASPT2) methods. For the four ionic states, we calculated the equilibrium geometries, adiabatic (T0) and vertical (Tv) excitation energies, and relative energies (Tv') at the geometry of the molecule at the CASPT2 level and the Cl-loss dissociation potential energy curves (PECs) at the CASPT2//CASSCF level. The computed oscillator strength f value for the X2A' ' <-- A2A' transition is very small, which is in line with the experimental fact that the A state has a long lifetime. The CASPT2 geometry and T0 value for the A2A' state are in good agreement with experiment. The CASPT2 Tv' values for the A2A', B2A' ', and C2A' states are in good agreement with experiment. The Cl-loss PEC calculations predict that the X2A' ', A2A', and C2A' states correlate to C2H3+ (XA1) and the BA' ' state to C2H3+ (1A' ') (the B2A' ' and C2A' PECs cross at R(C-Cl) approximately 2.24 A). Our calculations indicate that at 357 nm the X2A' ' state can undergo a transition to B2A' ' followed by a predissociation of B2A' ' by the repulsive C2A' state (via the B/C crossing), leading to C2H3+ (X1A1), and therefore confirm the experimentally proposed pathway for the photodissociation of X2A' ' at 357 nm. Our CASPT2 D0 calculations support the experimental fact that the X state does not undergo dissociation in the visible spectral region and imply that a direct dissociation of the A state to C2H3+ (X1A1) is energetically feasible.     

Spectral features of LO phonon sidebands in luminescence of free excitons in GaN

In the paper a combined experimental and theoretical investigation of the longitudinal optical phonon sidebands (PSBs) in the luminescence of free excitons in GaN at moderately high temperatures was reported. The spectral features, including line broadening, shift, and asymmetry of the one- and two-phonon PSBs, were revealed both experimentally and theoretically. It is found that the linewidth of the one-phonon PSB is surprisingly always larger than that of the two-phonon PSB in the interested temperature range. Moreover, the thermal broadening rates of the one- and two-phonon PSBs are considerably different. We adopted the Segall-Mahan theory [B. Segall and G. D. Mahan, Phys. Rev. 171, 935 (1968)] to compute the PSB spectra of the free excitons in GaN. Only one adjustable parameter, the effective mass of the holes, was used in the calculations. For the one-phonon PSB, an excellent agreement between theory and experiment is achieved when an adequate effective mass of the holes was used.     

Ab initio calculations of the electronic states of AsH2 including dissociation characteristics

Multireference configuration interaction calculations have been carried out for low-lying electronic states of AsH(2). Bending potentials for the ten lowest states of AsH(2) are obtained in C(2v) symmetry for As-H distances fixed at the the ground state equilibrium value of 2.845 a(0), as well as for the minimum energy path constrained to R(1) = R(2). The calculated equilibrium geometries for the X?(2)B(1) ground state and the A?(2)A(1) excited state agree very well with the previous experimental and theoretical results, whereas the data for the higher-lying states are obtained for the first time. Asymmetric potential energy surface (PES) cuts (at R(1) = 2.845 a(0), θ = 90.7°) and two-dimensional (2D) PESs for the lowest three states are also new. The calculated ab initio data are used for analysis of possible AsH(2) photodissociation channels and predissociation effects. It is shown that the A?(2)A(1)-X?(2)B(1) transition dipole moment decreases with increasing bending angle, which influences the intensity distribution in the A?(0,0,0)→X? emission spectrum (v(2)' bending series), shifting its maximum to smaller v(2)' quantum numbers.     

Spin-orbit mechanism of predissociation in the Wulf band of ozone

Previously calculated resonance widths of the ground vibrational levels in the electronic states 1 (3)A" ((3)A(2)) and 1 (3)A' ((3)B(2)), which belong to the Wulf band system of ozone, are significantly smaller than observed experimentally. We demonstrate that predissociation is drastically enhanced by spin-orbit coupling between 1 (3)A"/X (1)A' and 1 (3)A'/1 (3)A". Multistate quantum mechanical calculations using ab initio spin-orbit coupling matrix elements give linewidths of optically bright components of the right order of magnitude.     

Vibronic coupling in the superoxide anion: the vibrational dependence of the photoelectron angular distribution

We present a comprehensive photoelectron imaging study of the O(2)(X (3)Σ(g)(-),v(')=0-6)←O(2)(-)(X (2)Π(g),v(")=0) and O(2)(a?(1)Δ(g),v(')=0-4)←O(2)(-)(X (2)Π(g),v(")=0) photodetachment bands at wavelengths between 900 and 455 nm, examining the effect of vibronic coupling on the photoelectron angular distribution (PAD). This work extends the v(')=1-4 data for detachment into the ground electronic state, presented in a recent communication [R. Mabbs, F. Mbaiwa, J. Wei, M. Van Duzor, S. T. Gibson, S. J. Cavanagh, and B. R. Lewis, Phys. Rev. A 82, 011401(R) (2010)]. Measured vibronic intensities are compared to Franck-Condon predictions and used as supporting evidence of vibronic coupling. The results are analyzed within the context of the one-electron, zero core contribution (ZCC) model [R. M. Stehman and S. B. Woo, Phys. Rev. A 23, 2866 (1981)]. For both bands, the photoelectron anisotropy parameter variation with electron kinetic energy, β(E), displays the characteristics of photodetachment from a d-like orbital, consistent with the π(g)(?) 2p highest occupied molecular orbital of O(2)(-). However, differences exist between the β(E) trends for detachment into different vibrational levels of the X (3)Σ(g)(-) and a?(1)Δ(g) electronic states of O(2). The ZCC model invokes vibrational channel specific "detachment orbitals" and attributes this behavior to coupling of the electronic and nuclear motion in the parent anion. The spatial extent of the model detachment orbital is dependent on the final state of O(2): the higher the neutral vibrational excitation, the larger the electron binding energy. Although vibronic coupling is ignored in most theoretical treatments of PADs in the direct photodetachment of molecular anions, the present findings clearly show that it can be important. These results represent a benchmark data set for a relatively simple system, upon which to base rigorous tests of more sophisticated models.     

Time and frequency resolved dynamics of ArBr2

We report the first spectroscopic observation of and vibrational predissociation dynamics for ArBr(2). Measurements are reported for the linear and T-shaped isomers with time and frequency resolution near the Fourier limit of a 15 ps pulse. For the T-shaped isomer, the Ar-Br(2) bond energy D(0) for the B state, nu(')=19, is found to be 200 cm(-1), yielding a D(0)(X) value of 213 cm(-1). Product appearance rates are determined for nu(')=16-25 of the B state of ArBr(2). While the rate generally increases with increasing vibrational quantum number, the trend is not monotonic. Also, obtaining reproducible rates for any given vibrational level requires very careful control of the experimental conditions. The data suggest that ArBr(2) undergoes vibrational predissociation (VP) in the sparse intramolecular vibrational relaxation regime. These observations are consistent with theoretical calculations that show that T-shaped ArBr(2) undergoes VP in the sparse regime, such that lifetimes are strongly dependent on both the vibrational and rotational quantum numbers. As for ArI(2), a linear isomer of ArBr(2) is found to contribute a quasicontinuous background to the excitation spectra. Direct excitation of this continuum results in a very broad product vibrational distribution.     

Cross sections for electron impact excitation of the vibrationally resolved A 1Pi electronic state of carbon monoxide

The authors report new differential cross section measurements for electron impact excitation of the A (1)Pi(v(')) states of carbon monoxide. The energy range is 20-200 eV. They also reanalyze the A (1)Pi(v(')) manifold cross sections of Middleton et al. [J. Phys. B 26, 1743 (1993)] in order to provide a basis for comparison with our new vibrationally resolved differential cross sections. Excellent agreement is found between the two sets of measurements at all common energies. From 20 to 200 eV the present differential cross sections are extrapolated and integrated, and the corresponding integral excitation cross sections determined. New scaled Born integral cross sections, calculated as a part of the present study, are compared against these experimental integral cross sections, with excellent agreement being found for all the A (1)Pi(v(')=0-7)<--X (1)Sigma(g) (+)(v(")=0) transitions. In addition our scaled Born integral cross sections are found to be in excellent agreement between 300 and 1500 eV with those derived from the previous experiments of Lassettre and Skerbele [J. Chem. Phys. 54, 1597 (1971)] and of Zhong et al. [Phys. Rev. A 55, 1799 (1997)] and from near threshold to 15 eV with those derived from Zobel et al. [J. Phys. B 29, 813 (1996)] and Zetner et al. (J. Phys. B 31, 2395 (1998)].     

Intense-field modulation of NO2 multiphoton dissociation dynamics

We report on the dynamics of multiphoton excitation and dissociation of NO(2) at wavelengths between 395 and 420 nm and intensities between 4 and 10 TW cm(-2). The breakup of the molecule is monitored by NO A (2)Sigma(+)n(')=1,0-->X (2)Pi(r)n(")=0 fluorescence as a function of time delay between the driving field and a probe field which depletes the emission. It is found that generation of n(')=0 and 1 NO A (2)Sigma(+) results in different fluorescence modulation patterns due to the intense probe field. The dissociation dynamics are interpreted in terms of nuclear motions over light-induced potentials formed by coupling of NO(2) valence and Rydberg states to the applied field. Based on this model, it is argued that the time and intensity dependences of A (2)Sigma(+)n(')=0-->X (2)Pi(r)n(")=0 fluorescence are consistent with delayed generation of NO A (2)Sigma(+)n(')=0 via a light-induced bond-hardening brought about by the transient coupling of the dressed A (2)B(2) and Rydberg 3ssigma (2)Sigma(g) (+) states of the parent molecule. The increasingly prompt decay of A (2)Sigma(+)n(')=1-->X (2)Pi(r)n(")=0 fluorescence with increasing intensity, on the other hand, is consistent with a direct surface crossing between the X (2)A(1) and 3ssigma (2)Sigma(g) (+) dressed states to generate vibrationally excited products.     

Pressure broadening and fine-structure-dependent predissociation in oxygen B 3sigma(u)-, v = 0

Both laser-induced fluorescence and cavity ring-down spectral observations were made in the Schumann-Runge band system of oxygen, using a novel-type ultranarrow deep-UV pulsed laser source. From measurements on the very weak (0,0) band pressure broadening, pressure shift, and predissociation line-broadening parameters were determined for the B 3sigma(u)-, v = 0,F(i) fine-structure components for various rotational levels in O2. The information content from these studies was combined with that of entirely independent measurements probing the much stronger (0,10), (0,19), and (0,20) Schumann-Runge bands involving preparation of vibrationally excited O2 molecules via photolysis of ozone. The investigations result in a consistent set of predissociation widths for the B 3sigma(u)-, v = 0 state of oxygen.     

Quantum state-selected photodissociation dynamics of H2O: two-photon dissociation via the C̃ electronic state

The photodissociation dynamics of H(2)O via the C? state by two-photon excitation has been investigated using the H atom Rydberg tagging time-of-flight technique. The rotational resolved action spectrum of the C?←X? transition band has been measured. The line widths show a pronounced dependence on the parent rotational excitation in the C? state. The quantum state resolved OH product translational energy distributions and angular distributions have also been obtained. By carefully simulating these distributions, quantum state distributions of the OH product as well as the state-resolved angular anisotropy parameters were determined. The experimental results confirm the variation of two competitive predissociation pathways. A heterogeneous predissociation channel is mediated by rotational coupling to the B??(1)A(1) state associated with the a-axis (k(a)(')), and a homogeneous pathway arises from purely electronic coupling to the A??(1)B(1) state. We have also obtained the branching ratios of the OH(X) and OH(A) products, and related these to the C?→A? and C?→B? pathways. The branching ratios display a strong k(a)(') dependence.     

Intramolecular vibrational redistribution in the vibrational predissociation dynamics of He-I2

The intramolecular vibrational redistribution (IVR) process is investigated in wave packet simulations of the vibrational predissociation dynamics of He-I(2)(B,upsilon') in the region of high upsilon' levels, upsilon' = 35-65. The simulations indicate that for upsilon' < or = 45 the dynamics is dominated by direct predissociation, whereas for higher upsilon' levels the onset of IVR appears and becomes increasingly important. The IVR process occurs via coupling of the initial state in the upsilon' manifold to intermediate long-lived resonances belonging to the lower upsilon < upsilon' vibrational manifolds. The IVR dynamics manifests itself in multiexponential behavior and oscillations in the time-dependent population curves associated with the He-I(2)(B,upsilon') initial state, the He-I(2)(B,upsilon < upsilon') intermediate complexes, and the final product states. The population curves corresponding to the upsilon'- 1 intermediate resonances located below the He + I(2)(B,upsilon'-1,j=0) dissociation limit are analyzed. It is found that initial population is transferred to all the intermediate resonance states considered, including those more separated in energy from the initial one. The results obtained for population transfer between the initial and the intermediate states can be explained by the intensity of the matrix elements coupling the initial and the intermediate resonances, in combination with the Rabi's formula for population exchange between two coupled states.