Spectroscopic implications of the coupling of unquenched angular momentum to rotation in OH-containing complexes

A model is developed for the rotational energy levels and electric dipole transition intensities of nonlinear OH-containing complexes in which the OH is hydrogen bonded to its partner. Both the 2A' and 2A" electronic states arising from the lifting of the OH monomer electronic orbital degeneracy are explicitly included. Consequently, the model smoothly spans the entire range of the difference potential associated with the separation between these two states, and the model accounts for the partial quenching of the OH monomer electronic angular momentum in such complexes. The more familiar cases of completely unquenched and completely quenched electronic angular momentum are recovered in the limits of zero and very large difference potential, respectively. The sensitivity of rovibrational spectra to the value of the difference potential is investigated, and it is shown that spectra of reactant complexes reveal the extent of quenching, which must occur along the reaction coordinate as the system evolves from weakly interacting partners to addition product. The model is successfully applied to the analysis of the OH overtone spectrum of the OH-acetylene complex.     

Evidence for partial quenching of orbital angular momentum upon complex formation in the infrared spectrum of OH-acetylene

The entrance channel leading to the addition reaction between the hydroxyl radical and acetylene has been examined by spectroscopic characterization of the asymmetric CH stretching band of the pi-hydrogen bonded OH-acetylene reactant complex. The infrared action spectrum observed at 3278.6 cm(-1) (origin) consists of seven peaks of various intensities and widths, and is very different from those previously reported for closed-shell HF/HCl-acetylene complexes. The unusual spectrum arises from a partial quenching of the OH orbital angular momentum in the complex, which in turn is caused by a significant splitting of the OH monomer orbital degeneracy into (2)A(') and (2)A(") electronic states. The magnitude of the (2)A(')-(2)A(") splitting as well as the A rotational constant for the OH-acetylene complex are determined from the analysis of this b-type infrared band. The most populated OH product rotational state, j(OH)=9/2, is consistent with intramolecular vibrational energy transfer to the nu2 C triple bonded C stretching mode of the departing acetylene fragment. The lifting of the OH orbital degeneracy and partial quenching of its electronic orbital angular momentum indicate that the electronic changes accompanying the evolution of reactants into products have begun to occur in the reactant complex.     

Electronic quenching of OH A 2Sigma+ radicals in single collision events with molecular hydrogen: quantum state distribution of the OH X 2Pi products

We report a combined experimental and theoretical investigation of the nonreactive quenching channel resulting from electronic quenching of OH A 2Sigma+ by molecular hydrogen. The experiments utilize a pump-probe scheme to determine the OH X 2Pi population distribution following collisional quenching in a pulsed supersonic expansion. The pump laser excites OH A 2Sigma+ (nu'=0, N'=0), which has a significantly reduced fluorescence lifetime due to quenching by H2. The probe laser monitors the OH X 2Pi (nu", N") population via laser-induced fluorescence on various A-X transitions under single collision conditions. The experiments reveal a high degree of rotational excitation (N") of the quenched OH X 2Pi products observed in nu"=1 and 2 as well as a pronounced propensity for quenching into the Pi(A') Lambda-doublet level. These experiments have been supplemented by extensive multireference, configuration-interaction calculations aimed at exploring the topology of the relevant potential energy surfaces. Electronic quenching of OH A 2Sigma+ by H2 proceeds through conical intersections between two potentials of A' reflection symmetry (in planar geometry) that correlate with the electronically excited A 2Sigma+ and ground X 2Pi states of OH. The conical intersections occur in high-symmetry geometries, in which the O side of OH points toward H2. Corroborating and extending earlier work of Hoffman and Yarkony [J. Chem. Phys. 113, 10091 (2000)], these calculations reveal a steep gradient away from the OH-H2 conical intersection as a function of both the OH orientation and interfragment distance. The former will give rise to a high degree of OH rotational excitation, as observed for the quenched OH X 2Pi products.     

Pulsed field ionization electron spectroscopy and molecular structure of aluminum uracil

Al-uracil (Al-C4H4N2O2) was synthesized in a laser-vaporization supersonic molecular beam source and studied with pulsed field ionization-zero electron kinetic energy (ZEKE) photoelectron spectroscopy and density functional theory (DFT). The DFT calculations predicted several low-energy Al-uracil isomers with Al binding to the diketo, keto-enol, and dienol tautomers of uracil. The ZEKE spectroscopic measurements of Al-uracil determined the ionization energy of 43 064(5) cm-1 [or 5.340(6) eV] and a vibrational mode of 51 cm-1 for the neutral complex and several vibrational modes of 51, 303, 614, and 739 cm-1 for the ionized species. Combination of the ZEEK spectrum with the DFT and Franck-Condon factor calculations determined the preferred isomeric structure and electronic states of the Al-uracil complex. This isomer is formed by Al binding to the O4 atom of the diketo tautomer of uracil and has a planar Cs symmetry. The ground electronic states of the neutral and ionized species are 2A' ' and 1A', respectively. The 2A' ' neutral state has a slightly shorter Al-O4 distance than the 1A' ion state. However, the 1A' ion state has stronger metal-ligand binding compared to the 2A' ' state. The increased Al-O4 distance from the 2A' ' state to the 1A' state is attributed to the loss of the pi binding interaction between Al and O4 in the singlet ion state, whereas the increased metal-ligand binding strength is due to the additional charge-dipole interaction in the ion that surpasses the loss of the pi orbital interaction.     

Nonadiabatic quantum reactive scattering of the OH(A 2Σ+) + D2

The seams of conical intersection exist between the ground (1 (2)A(')) and the first-excited (2 (2)A(')) electronic potential energy surfaces (PESs) of OH(A (2)Σ(+),X (2)Π) + H(2) system. This intersection induces the nonadiabatic quenching of OH(A (2)Σ(+)) by D(2). We present nonadiabatic quantum dynamics study for OH(A (2)Σ(+)) + D(2) on new five-dimensional coplanar PESs. The ab initio calculations of PESs are based on multireference configuration interaction (MRCI)/aug-cc-pVQZ level. A back-propagation neural network is utilized to fit the PESs and nonadiabatic coupling. High degrees of rotational excitation of quenched OH(X (2)Π) products are found in nonreactive quenching channel, and the quenched D(2) products are vibrationally excited up to quantum number v(2) (')=8. The theoretical results of nonadiabatic time-dependent wave-packet calculation are in good agreement with the existing experimental data.     

Half-sandwich structure of cyclopentadienyl dialuminum [Al2(eta5-C5H5)] from pulsed-field ionization electron spectroscopy and ab initio calculations

Cyclopentadienyl dialuminum [Al2Cp, Cp = C5H5] was prepared in a pulsed laser ablation cluster beam source and identified with a time-of-flight photoionization mass spectrometer. The high-resolution electron spectrum of this complex was obtained using pulsed-field ionization zero electron kinetic energy (ZEKE) photoelectron spectroscopy. Three isomeric structures with two Al atoms residing on the same or opposite sites of the Cp plane were predicted by second-order M?ller-Plesset perturbation theory. A half-sandwich structure with an aluminum dimer perpendicular to the Cp plane was identified by the experiment. The ground electronic states of the neutral and ionized species are 2A' ' in Cs symmetry and 1A1 in C5v symmetry, respectively. In both the neutral and ionic states, one of the Al2 atoms binds with five carbons, and the metal-ligand bonding consists of orbital and electrostatic contributions. Ionization of the 2A' ' neutral state enhances the metal-ligand bonding but weakens the metal-metal interaction.     

REMPI-TOF studies of the translational anisotropy and the polarization of the O ((1)D2) photofragment angular momentum following ozone photolysis at 298 nm

The translational anisotropy and the polarization of the electronic angular momentum of the O ((1)D2) fragment produced from the 298 nm photodissociation of ozone have been determined using resonance enhanced multiphoton ionization (REMPI) in conjunction with time-of-flight mass spectrometry (TOFMS). The translational anisotropy parameter beta, which is necessarily averaged over the O2 co-fragment rotational distribution, is measured to be 1.08 +/- 0.04. This is consistent with that expected for the (1)B2 <-- (1)A1 transition within an impulsive model if the tangential velocity associated with the zero point motion of the bend is constricted to opening the bond angle. Molecular frame polarization parameters of rank up to k = 4 have been extracted for the O ((1)D2) fragment and the calculated m(J) populations show a strong preference for the absolute value(m(J)) = 1 states. A small coherence term is also observed, a manifestation of the nuclear geometry of the dissociating molecule and the existence of possible non-adiabatic processes in the exit channel. The orientation associated with the mapping of the photon helicity onto the O ((1)D2) electronic angular momentum distribution was observed to have been quenched. However, the parameter gamma1', which describes the contribution to the orientation from a coherent superposition of a parallel and perpendicular excitation where the photofragment angular momentum lies perpendicular to both the recoil velocity and to the transition dipole moment, was determined to be -0.06.     

Cl-loss and H-loss dissociations in low-lying electronic states of the CH3Cl+ ion studied using multiconfiguration second-order perturbation theory

To examine the experimentally suggested scheme of the pathways for Cl- and H-loss dissociations of the CH(3)Cl(+) ion in the X(2)E (1(2)A', 1(2)A' '), A(2)A(1) (2(2)A'), and B(2)E (3(2)A', 2(2)A") states, the complete active space-self-consistent field (CASSCF) and multiconfiguration second-order perturbation theory (CASPT2) calculations with an atomic natural orbital (ANO) basis were performed for the 1(2)A' (X(2)A'), 1(2)A", 2(2)A', and 2(2)A'" states. The potential energy curves describing dissociation from the four C(s) states were obtained on the basis of the CASSCF partial geometry optimization calculations at fixed C-Cl or C-H distance values, followed by the CASPT2 energy calculations. The electronic states of the CH3(+) and CH(2)Cl(+) ions produced by Cl-loss and H-loss dissociation, respectively, were carefully determined. Our calculations confirm the following experimental facts: Cl-loss dissociation occurs from the 1(2)A' (X(2)A'), 1(2)A", and 2(2)A' states (all leading to CH3(+) (X(1)A(1)') + Cl), and H-loss dissociation does not occur from 2(2)A'. The calculations indicate that H-loss dissociation occurs from the 1(2)A' and 1(2)A' ' states (leading to CH(2)Cl(+) (X(1)A(1)) + H and CH(2)Cl(+) (1(3)A") + H, respectively). The calculations also indicate that H-loss dissociation occurs (with a barrier) from the 2(2)A" state (leading to CH(2)Cl(+) (1(1)A") + H), supporting the observation of direct dissociation from the B state to CH(2)Cl(+) and that Cl-loss dissociation occurs from the 2(2)A" state (leading to CH3(+) (1(3)A") + Cl), not supporting the previously proposed Cl-loss dissociation of the B state via internal conversion of B to A. The predicted appearance potential values for CH3(+) (X(1)A(1)') and CH(2)Cl(+) (X(1)A(1)) are in good agreement with the experimental values.     

Time-dependent quantum study of the kinetics of the H(2S) + FO(2II) OH(2II) + F(2P) reaction

Quantum mechanical wave packet calculations are carried out for the H((2)S) + FO((2)II) --> OH((2)II) + F((2)P) reaction on the adiabatic potential energy surface of the ground (3)A' triplet state. The state-to-state and state-to-all reaction probabilities for total angular momentum J = 0 have been calculated. The probabilities for J > 0 have been estimated from the J = 0 results by using J-shifting approximation based on a capture model. Then, the integral cross sections and initial state-selected rate constants have been calculated. The calculations show that the initial state-selected reaction probabilities are dominated by many sharp peaks. The reaction cross section does not manifest any sharp oscillations and the initial state-selected rate constants are sensitive to the temperature.     

Quantum dynamics of coupled translational and rotational motions of H2 inside C60

We report rigorous quantum calculations of the translation-rotation (T-R) eigenstates of the H2 molecule in C60. The resulting level structure can be explained in terms of a few dominant features. These include the coupling between the orbital and the rotational angular momenta of H2 to give the total angular momentum lambda, and the splitting of the sevenfold degeneracy of T-R levels with lambda=3 by the nonsphericity of C60, according to the rules of the icosahedral I h group.     

Ab initio study on the decomposition of first excited state HOOO radicals

The HOOO radical plays a crucial role in atmospheric processes involving the OH radical and O(2) molecule. We present an ab initio molecular orbital theory study on the decomposition reaction of the first excited state HOOO((2)A') with respect to OH and O(2). The geometries and harmonic vibrational frequencies of all stationary points are calculated at the CASSCF and MRCI levels of theory in conjunction with the 6-31+G(d,p) basis set. The potential energy profile of the decomposition reaction is studied at the CASSCF/6-31+G(d,p) level of theory, in which the complete valence orbitals and electrons are included in the active space. The energies of the potential energy profile are further refined at the CASPT2 and MRCI levels of the theory. Additionally, we have determined the interesting reaction process: the HOOO((2)A') radical with C(s) symmetry does not dissociate to OH((2)Pi) and O(2)((3)Sigma(-)(g)) directly as this is forbidden by orbital symmetry, but dissociates to OH((2)Pi) and O(2)((3)Sigma(-)(g)) via the change in symmetry from C(s) to C(infinity v) symmetry with a low barrier.     

Probing photophysical and photochemical processes of benzoic acid from ab initio calculations

The CASSCF and DFT methods have been used to determine geometric and electronic structures of the benzoic acid monomer in the S(0), S(1), S(2), T(1), and T(2) electronic states. The S(1)/T(2)/T(1) three-surface intersection was found by the state-averaged CASSCF calculations, which, in combination with features of the five lowest electronic states, provides new insights into photophysical processes of the benzoic acid monomer. The potential energy profiles of the alpha C-C and C-O bond fissions as well as decarboxylation reaction in different electronic states have been determined for the benzoic acid monomer. The alpha C-O bond cleavage starts from the T(2) state and leads to the fragments of C(6)H(5)CO(X(2)A') and OH(X(2)Pi) in the ground state, which is predicted to be the most possible channel upon photoexcitation of the benzoic acid monomer at 270 nm or shorter wavelengths.     

Electronic quenching of OH A 2Sigma+ radicals in single collision events with H2 and D2: a comprehensive quantum state distribution of the OH X 2Pi products

A pump-probe laser-induced fluorescence technique has been used to examine the nascent OH X (2)Pi product state distribution arising from non-reactive quenching of electronically excited OH A (2)Sigma(+) by molecular hydrogen and deuterium under single-collision conditions. The OH X (2)Pi products were detected in v'=0, 1 and 2; the distribution peaks in v'=0 and decreases monotonically with increasing vibrational excitation. In all vibrational levels probed, the OH X (2)Pi products are found to be highly rotationally excited, the distribution peaking at N'=15 when H(2) was used as the collision partner and N'=17 for D(2). A marked propensity for production of Pi(A') Lambda-doublet levels was observed, while both OH X (2)Pi spin-orbit manifolds were equally populated. These observations are interpreted as dynamical signatures of the nonadiabatic passage of the OH + H(2)/D(2) system through the seams of conical intersection that couple the excited state (2 (2)A') and ground state (1 (2)A') surfaces.     

An animated visualization of orbital angular momentum and spin‐orbit coupling

This paper presents an approach toward visualizing a complex orbital based on animation using a time‐dependent phase factor. This makes orbital angular momentum clearly visible, in a way that reflects the nature of the orbital angular momentum wavefunction. Visualization of this quantity is also useful for examining the effects of spin‐orbit coupling (SOC), in which higher orbital angular momentum states are admixed into the orbital; in this case, however, scaling of one phase‐component is needed. The phase orientation of a complex orbital, which is generally not guaranteed by the SCF procedure, must be considered when doing this. The method of visualization presented here may prove useful when analyzing properties where SOC is important, such as magnetic resonance parameters. Animated visualizations are performed, and compared with the method of phase‐colored isosurfaces, first for a model p‐orbital to explain the idea, and then for the singly‐occupied molecular orbitals of two small doublet radicals.     

Relaxation theory of the electronic spin of a complexed paramagnetic metal ion in solution beyond the Redfield limit

The relaxation of the electronic spin S of a paramagnetic metal ion with fully quenched orbital angular momentum in its ground state is investigated in an external magnetic field through a systematic study of the time correlation functions governing the evolution of the statistical operator (density matrix). Let omega0 be the Larmor angular frequency of S. When the relaxation is induced by a time-fluctuating perturbing Hamiltonian hH1(t) of time correlation tauc, it is demonstrated that after a transient period the standard Redfield approximation is relevant to calculate the evolution of the populations of the spin states if parallelH1 parallel2tauc2/(1+omega0(2)tauc2)<1 and that this transient period becomes shorter than tauc at sufficiently high field for a zero-field splitting perturbing Hamiltonian. This property, proven analytically and confirmed by numerical simulation, explains the surprising success of several simple expressions of the longitudinal electronic relaxation rate 1/T1e derived from the Redfield approximation well beyond its expected validity range parallelH1 paralleltauc<1. It has favorable practical consequences on the interpretation of the paramagnetic relaxation enhancement of nuclei used for structural and dynamic studies.     

Virtual free ion magnetism and the absence of Jahn-Teller distortion in a linear two-coordinate complex of high-spin iron(II)

M?ssbauer spectroscopy and dc magnetization measurements have been used to characterize the low temperature magnetism of a rigorously linear, two-coordinate complex of high-spin Fe(II), Fe[(C(Si(CH3)3]2 (1). The local C-Fe-C chromophore of 1 exhibits novel slow, single-ion paramagnetic relaxation and fully resolved magnetic hyperfine splitting of its zero field M?ssbauer spectrum over the range approximately 100 to approximately 50K. The hyperfine field at 4.2 K is 152 T! This is the largest magnetic hyperfine field observed for iron to date regardless of spin, oxidation state, or coordination environment. This observation is attributable to the large unquenched orbital angular momentum corresponding to the degenerate ground (dxy, dx2-y2) orbital pair of 1 in local Dinfinityh symmetry. Maintenance of the ground-state degeneracy is required by the Jahn-Teller theorem leading to the unprecedented result that the magnitude of the magnetic moment of 1's 5Deltag ground state is essentially that of the parent free ion (5D4) ground term.     

Basis set convergence of explicitly correlated double-hybrid density functional theory calculations

The basis set convergence of explicitly correlated double-hybrid density functional theory (DFT) is investigated using the B2GP-PLYP functional. As reference values, we use basis set limit B2GP-PLYP-F12 reaction energies extrapolated from the aug(')-cc-pV(Q+d)Z and aug(')-cc-pV(5+d)Z basis sets. Explicitly correlated double-hybrid DFT calculations converge significantly faster to the basis set limit than conventional calculations done with basis sets saturated up to the same angular momentum (typically, one "gains" one angular momentum in the explicitly correlated calculations). In explicitly correlated F12 calculations the VnZ-F12 basis sets converge faster than the orbital A(')VnZ basis sets. Furthermore, basis set convergence of the MP2-F12 component is apparently faster than that of the underlying Kohn-Sham calculation. Therefore, the most cost-effective approach consists of combining the MP2-F12 correlation energy from a comparatively small basis set such as VDZ-F12 with a DFT energy from a larger basis set such as aug(')-cc-pV(T+d)Z.     

Product spin-orbit state resolved dynamics of the H+H2O and H+D2O abstraction reactions

The product state-resolved dynamics of the reactions H+H(2)O/D(2)O-->OH/OD((2)Pi(Omega);v',N',f )+H(2)/HD have been explored at center-of-mass collision energies around 1.2, 1.4, and 2.5 eV. The experiments employ pulsed laser photolysis coupled with polarized Doppler-resolved laser induced fluorescence detection of the OH/OD radical products. The populations in the OH spin-orbit states at a collision energy of 1.2 eV have been determined for the H+H(2)O reaction, and for low rotational levels they are shown to deviate from the statistical limit. For the H+D(2)O reaction at the highest collision energy studied the OD((2)Pi(3/2),v'=0,N'=1,A') angular distributions show scattering over a wide range of angles with a preference towards the forward direction. The kinetic energy release distributions obtained at 2.5 eV also indicate that the HD coproducts are born with significantly more internal excitation than at 1.4 eV. The OD((2)Pi(3/2),v'=0,N'=1,A') angular and kinetic energy release distributions are almost identical to those of their spin-orbit excited OD((2)Pi(1/2),v'=0,N'=1,A') counterpart. The data are compared with previous experimental measurements at similar collision energies, and with the results of previously published quasiclassical trajectory and quantum mechanical calculations employing the most recently developed potential energy surface. Product OH/OD spin-orbit effects in the reaction are discussed with reference to simple models.     

Long-range interactions between an atom in its ground S state and an open-shell linear molecule

Theory of long-range interactions between an atom in its ground S state and a linear molecule in a degenerate state with a nonzero projection of the electronic orbital angular momentum is presented. It is shown how the long-range coefficients can be related to the first and second-order molecular properties. The expressions for the long-range coefficients are written in terms of all components of the static and dynamic multipole polarizability tensor, including the nondiagonal terms connecting states with the opposite projection of the electronic orbital angular momentum. It is also shown that for the interactions of molecules in excited states that are connected to the ground state by multipolar transition moments additional terms in the long-range induction energy appear. All these theoretical developments are illustrated with the numerical results for systems of interest for the sympathetic cooling experiments: interactions of the ground state Rb((2)S) atom with CO((3)Π), OH((2)Π), NH((1)Δ), and CH((2)Π) and of the ground state Li((2)S) atom with CH((2)Π).     

F-loss and H-loss dissociations in low-lying electronic states of the CH3F+ ion studied using multiconfiguration second-order perturbation theory

Complete active space self-consistent field (CASSCF) and multiconfiguration second-order perturbation theory (CASPT2) calculations with an atomic natural orbital basis were performed for the 1(2)A', 1(2)A', 2(2)A', 2(2)A', and 3(2)A' (X2E, A2A1, and B2E) states of the CH3F+ ion. The 1(2)A' state is predicted to be the ground state, and the C(s)-state energy levels are different from those of the CH3Cl+ ion. The 2(2)A' (A2A1) state is predicted to be repulsive, and the calculated adiabatic excitation energies for 2(2)A' and 3(2)A' are very close to the experimental value for the B state. The CASPT2//CASSCF potential energy curves (PECs) were calculated for F-loss dissociation from the five C(s) states and H-loss dissociation from the 1(2)A', 1(2)A', and 2(2)A' states. The electronic states of the CH3+ and CH2F+ ions as the dissociation products were carefully determined by checking the energies and geometries of the asymptote products, and appearance potentials for the two ions in different states are predicted. The F-loss PEC calculations for CH3F+ indicate that F-loss dissociation occurs from the 1(2)A', 1(2)A', and 2(2)A' states [all correlating with CH3+(X1A1')], which supports the experimental observations of direct dissociation from the X and A states, and that direct F-loss dissociation can occur from the two Jahn-Teller component states of B2E, 2(2)A' and 3(2)A' [correlating with CH3+(1(3)A') and CH3+(1(3)A'), respectively]. Some aspects of the 3(2)A' Cl-loss PEC of the CH3Cl+ ion are inferred on the basis of the calculation results for CH3F+. The H-loss PEC calculations for CH3F+ indicate that H-loss dissociation occurs from the 1(2)A', 1(2)A', and 2(2)A' states [correlating with CH2F+(1(3)A'), CH2F+(X1A1), and CH2F+(1(1)A'), respectively], which supports the observations of direct dissociation from the X and B states. As the 2(2)A' H-loss PEC of CH3Cl+, the 2(2)A' H-loss PEC of CH3F+ does not lead to H + CH2X+, but the PECs of the two ions represent different types of reactions.