Bound state spectroscopy of NH-He

The NH-He van der Waals complex was characterized via laser excitation of bands associated with the NH A (3)Pi-X (3)Sigma(-) transition. It was demonstrated that the ground state supports a bound level with a rotational constant of B"=0.334(2) cm(-1). These results are in agreement with the predictions of recent high-level theoretical calculations. Spin-orbit predissociation of the excited complex was observed, and the spectra yield insights regarding the NH(A)+He potential energy surfaces.     

Photoinduced Rydberg ionization spectroscopy of the B state of benzonitrile cation

Photoinduced Rydberg ionization (PIRI) spectra of the second excited electronic state of benzonitrile cation were recorded via the origin and 6a1 and 6b1 vibrational levels of the cation ground electronic state. This B<--X transition was verified to be a forbidden 2B2<--2B1 transition with an origin at 17,225 cm-1 above the ground ionic state. By the use of vibronic coupling calculations, as well as symmetry analysis and comparison of the PIRI spectra via different ground vibrational levels, a nearly complete assignment of the vibrational structure was made, and the vibrational frequencies of the B 2B2 state of benzonitrile cation were obtained based on the assignments. Comparisons of the experimental spectra with simulations from the vibronic structure calculations are also used to validate the theoretical procedures used in the simulations.     

Observation of bound-free transitions of the linear Ar...I2(X,v"=0) complex in and above the I2 B-X spectral region

Laser-induced fluorescence and action spectroscopy experiments were performed to identify the origin of the Ar...I(2) continuum signals observed in and above the I(2) B-X spectral region. We have verified that these signals arise from transitions of the linear Ar...I(2) (X,v"=0) complex. The data provides no evidence that the excited state complexes undergo a one-atom caging mechanism when prepared above the I(2)(B) dissociation limit, Ar...I(2) (B)*-->Ar+I+I*-->Ar+I(2)(B,v'). Instead, our results indicate that the continuum signals result from bound-free transitions of the linear Ar...I(2) X,v(")=0) complex to the inner repulsive walls of numerous Ar+I(2)(B,v') intermolecular potentials. The bound-free continuum signal associated with transitions to each Ar+I(2)(B,v') potential spans an energy region >700 cm(-1). We have found that the continuum signals turn-on 250(2)cm(-1) above the corresponding I(2) B-X,v'-0 band origin, and this energy represents the binding energy of the linear Ar...I(2) (X,v"=0) conformer, D(0) (")(L)=250(2)cm(-1).     

Transition state structure and energetics of the N(2)O + X (X = Cl,Br) reactions

The structural and vibrational properties of the transition state of the N(2)O + X (X = Cl,Br) reactions have been characterized by ab initio methods using density functional theory. We have employed Becke's hybrid functional (B3LYP), and transition state optimizations were performed with 6-31G(d), 6-311G(2d,2p), 6-311+G(3d,2p), and 6-311+G(3df,2p) basis sets. For the chlorine atom reaction the coupled-cluster method (CCSD(T)) with 6-31G(d) basis set was also used. All calculations resulted in transition state structures with a planar cis arrangement of atoms for both reactions. The geometrical parameters of transition states at B3LYP are very similar, and the reaction coordinates involve mainly the breaking of the N-O bond. At CCSD(T)/6-31G(d) level a contribution of the O-Cl forming bond is also observed in the reaction coordinate. In addition, several highly accurate ab initio composite methods of Gaussian-n (G1, G2, G3), their variations (G2(MP2), G3//B3LYP), and complete basis set (CBS-Q, CBS-Q//B3LYP) series of models were applied to compute reaction energetics. All model chemistries predict exothermic reactions. The G3 and G2 methods result in the smallest deviations from experiment, 1.8 and 0 kcal mol(-1), for the enthalpies of reaction for N(2)O reaction with chlorine and bromine, respectively. The G3//B3LYP and G1 methods perform best among the composite methods in predicting energies of the transition state, with a deviation of 1.9 and 3.0 kcal mol(-1), respectively, in the activation energies for the above processes. However, the B3LYP/6-311+G(3df,2p) method gives smaller deviations of 0.4 and -1.0 kcal mol(-1), respectively. The performance of the methodologies applied in predicting transition state energies was analyzed.     

High resolution laser excitation spectroscopy of the B2E-X2A1 transitions of calcium and strontium monoborohydride

High resolution spectra of the B2E-X2A1 transitions of CaBH4 and SrBH4 have been recorded using laser excitation spectroscopy in a laser ablation/molecular jet source. Because of rotational cooling in the molecular jet and nuclear spin statistics, transitions arising from only the K'=1<--K"=0, K'=2<--K"=1, and K'=0<--K"=1 subbands have been observed. For each molecule, an analysis of the data using 2E and 2A1 symmetric top Hamiltonians yielded rotational, spin-orbit, and spin-rotation parameters for the observed states. For both molecules the rotational constants compare well with those calculated for a tridentate borohydride structure. A large reduction in the spin-orbit splitting and in the metal-ligand separation for each molecule indicates an increase in the amount of d atomic orbital character in the first excited 2E states of the monoborohydrides as compared to the monomethyl derivatives. For each molecule no evidence of internal rotation of the BH4- ligand was found. A change in the magnitude and sign of the spin-rotation constant epsilon1 confirms an energy reordering of the first excited 2E and 2A1 states in both CaBH4 and SrBH4 as compared to CaCH3 and SrCH3. The data also suggest that the B2E1/2 rotational energy levels of CaBH4 may be perturbed by a vibronic component of the A2A1 state.     

Transition states for the dimerization of 1,3-cyclohexadiene: a DFT, CASPT2, and CBS-QB3 quantum mechanical investigation

Quantum mechanical calculations using restricted and unrestricted B3LYP density functional theory, CASPT2, and CBS-QB3 methods for the dimerization of 1,3-cyclohexadiene (1) reveal several highly competitive concerted and stepwise reaction pathways leading to [4 + 2] and [2 + 2] cycloadducts, as well as a novel [6 + 4] ene product. The transition state for endo-[4 + 2] cycloaddition (endo-2TS, DeltaH(double dagger)(B3LYP(0K)) = 28.7 kcal/mol and DeltaH(double dagger)(CBS-QB3(0K)) = 19.0 kcal/mol) is not bis-pericyclic, leading to nondegenerate primary and secondary orbital interactions. However, the C(s) symmetric second-order saddle point on the B3LYP energy surface is only 0.3 kcal/mol above endo-2TS. The activation enthalpy for the concerted exo-[4 + 2] cycloaddition (exo-2TS, DeltaH(double dagger)(B3LYP(0K)) = 30.1 kcal/mol and DeltaH(double dagger)(CBS-QB3(0K)) = 21.1 kcal/mol) is 1.4 kcal/mol higher than that of the endo transition state. Stepwise pathways involving diallyl radicals are formed via two different C-C forming transition states (rac-5TS and meso-5TS) and are predicted to be competitive with the concerted cycloaddition. Transition states were located for cyclization from intermediate rac-5 leading to the endo-[4 + 2] (endo-2) and exo-[2 + 2] (anti-3) cycloadducts. Only the endo-[2 + 2] (syn-3) transition state was located for cyclization of intermediate meso-5. The novel [6 + 4] "concerted" ene transition state (threo-4TS, DeltaH(double dagger)(UB3LYP(0K)) = 28.3 kcal/mol) is found to be unstable with respect to an unrestricted calculation. This diradicaloid transition state closely resembles the cyclohexadiallyl radical rather than the linked cyclohexadienyl radical. Several [3,3] sigmatropic rearrangement transition states were also located and have activation enthalpies between 27 and 31 kcal/mol.     

Photodissociation of vibrationally excited SH and SD radicals at 288 and 291 nm: the S(1D2) channel

Ultraviolet photodissociation of SH (X 2Pi, upsilon"=2-7) and SD (X 2Pi, upsilon"=3-7) has been studied at 288 and 291 nm, using the velocity map imaging technique to probe the angular and speed distributions of the S(1D2) products. Photodissociation cross sections for the A 2Sigma+<--X 2Pi(upsilon") and 2Delta<--X 2Pi(upsilon") transitions have been obtained by ab initio calculations at the CASSCF-MRSDCI/aug-cc-pV5Z level of theory. Both the experimental and theoretical results show that SH/SD photodissociation from X 2Pi (upsilon"相似文献   

Laser induced fluorescence spectroscopy of the C3N radical

Electronic spectra of the C3N radical have been observed for the first time in the near ultraviolet wavelength region by laser induced fluorescence (LIF) spectroscopy. Seventeen vibronic bands of the B 2Pii-X 2Sigma+ electronic transition system of C3N were identified in LIF spectra of products in a discharge of HC3N. The origin of the B 2Pii state was determined to be 27,929.985(1) cm(-1) from rovibrational analyses. It was found that observations of two types of 2Sigma vibronic levels, which have 2Sigma+ and 2Sigma+/- symmetries originated from excitations of the nu4 trans-bending mode (omega4=369.1(20) cm(-1)) with a large Renner-Teller (RT) interaction (epsilon4=-0.1549(50)), and the nu5 cis-bending mode (omega5=163.24(84) cm(-1)) with a small Renner-Teller interaction (epsilon5=-0.0503(68)), respectively. Vibronic levels, with excitations of the C-C stretching (omega3=869.7 cm(-1)) mode, were also identified. The spin-orbit interaction constant was determined to be Aso=-36.7(50) cm(-1) from the RT analysis. In dispersed fluorescence spectra from B 2Pii, vibrational structures of the low-lying electronically excited A 2Pii state were clearly observed with a strong progression due to the nu3' mode, together with those of the X 2Sigma+ state with weak intensities. The origin of A 2Pii, T0=1844(3) cm(-1), and the vibrational frequencies, omega3'=883(3) cm(-1) and omega5'=121(3) cm(-1) for A 2Pii, and omega3"=1054(3) cm(-1), omega4"=405(3) cm(-1), and omega5"=131(3) cm(-1) for X 2Sigma+, were determined. Time profiles of fluorescence from B 2Pii have short (50-200 ns) and long (>1 micros) decay components with quantum beats, indicating that there is a competition between radiative decay and the nonradiative internal conversion to vibrationally highly excited A 2Pii and X 2Sigma+.     

Transition state for the gas-phase reaction of uranium hexafluoride with water

Density functional theory and small-core, relativistic pseudopotentials were used to look for symmetric and asymmetric transition states of the gas-phase hydrolysis reaction of uranium hexafluoride, UF 6, with water. At the B3LYP/6-31G(d,p)/SDD level, an asymmetric transition state leading to the formation of a uranium hydroxyl fluoride, U(OH)F 5, and hydrogen fluoride was found with an energy barrier of +77.3 kJ/mol and an enthalpy of reaction of +63.0 kJ/mol (both including zero-point energy corrections). Addition of diffuse functions to all atoms except uranium led to only minor changes in the structures and relative energies of the reacting complex and transition state. However, a significant change in the structure of the product complex was found, significantly reducing the enthalpy of reaction to +31.9 kJ/mol. Similar structures and values were found for PBE0 and MP2 calculations with this larger basis set, supporting the B3LYP results. No symmetric transition state leading to the direct formation of uranium oxide tetrafluoride, UOF 4, was found, indicating that the reaction under ambient conditions likely includes several more steps than the mechanisms commonly mentioned. The transition state presented here appears to be the first published transition state for the important gas-phase reaction of UF 6 with water.     

X, A, B, C, and D states of the C6H5F+ ion studied using multiconfiguration wave functions

Electronic states of the C6H5F+ ion have been studied within C2v symmetry by using the complete active space self-consistent field (CASSCF) and multiconfiguration second-order perturbation theory (CASPT2) methods in conjunction with an atomic natural orbital basis. Vertical excitation energies (Tv) and relative energies (Tv') at the ground-state geometry of the C6H5F molecule were calculated for 12 states. For the five lowest-lying states, 1(2)B1, 1(2)A2, 2(2)B1, 1(2)B2, and 1(2)A1, geometries and vibrational frequencies were calculated at the CASSCF level, and adiabatic excitation energies (T0) and potential energy curves (PEC) for F-loss dissociations were calculated at the CASPT2//CASSCF level. On the basis of the CASPT2 T0 calculations, we assign the X, A, B, C, and D states of the ion to 1(2)B1, 1(2)A2, 2(2)B1, 1(2)B2, and 1(2)A1, respectively, which supports the suggested assignment of the B state to (2)(2)B1 by Anand et al. based on their experiments. Our CASPT2 Tv and Tv' calculations and our MRCI T0, Tv, and Tv' calculations all indicate that the 2(2)B1 state of C6H5F+ lies below 1(2)B2. By checking the relative energies of the asymptote products and checking the fragmental geometries and the charge and spin density populations in the asymptote products along the CASPT2//CASSCF PECs, we conclude that the 1(2)B1, 1(2)B2, and 1(2)A1 states of C6H5F+ correlate with C6H5+ (1(1)A1) + F (2P) (the first dissociation limit). The energy increases monotonically along the 1(2)B1 PEC, and there are barriers and minima along the 1(2)B2 and 1(2)A1 PECs. The predicted appearance potential value for C6H5+ (1(1)A1) is very close to the average of the experimental values. Our CASPT2//CASSCF PEC calculations have led to the conclusion that the 1(2)A2 state of C6H5F+ correlates with the third dissociation limit of C6H5+ (1(1)A2) + F (2P), and a preliminary discussion is presented.     

Spectroscopic characterization of the C2-Ne van der Waals complex

Binary complexes of C2 with rare-gas atoms (C2-Rg) have attracted theoretical interest as their potential-energy surfaces are predicted to support linear equilibrium geometries, without the local minimum for the T-shaped geometry that would be expected using a standard pair-potential model. In the present work we have explored the properties of C2-Ne using laser-induced fluorescence detection of the D 1Sigmau +-X 1Sigmag + transition. Bands of the complex were observed in association with the monomer 0-0 and 1-1 transitions. Rotationally resolved data yielded rotational constants of B'=0.099(3) cm(-1) and B"=0.100(3) cm(-1) for the excited and ground states, respectively. Analysis of the rovibrational energy-level structure for C2(D)-Ne indicates that the complex has a linear equilibrium structure with a barrier to internal rotation of approximately 15 cm(-1). Data for the ground state validate a recent high-level ab initio calculation of the potential-energy surface for C2(X)-Ne.     

Radiative lifetimes for the B1piu state of the Na2 molecule

A study of the radiative lifetimes calculation of the Na2 B1piu state is presented. RKR electronic potentials are considered. The studied vibrational levels are for v' = 0-33 (B1piu) and v" = 0-65 (chi1sigmag+). The rotation is considered for values of J' = 1-225 (B1piu). The Einstein emission coefficients are calculated for the specified B1piu rovibrational levels (for Q line and R, P lines, for all ground state vibrational levels). With the inverse of Einstein emission coefficients sum, the radiative lifetimes are calculated. These calculated lifetimes are in good agreement with the experimental and previously calculated (with RKR potentials) lifetimes, but now great extension of considered rovibrational levels is considered. The bound-free contribution is irrelevant for Na2 lifetimes of the B1piu state. The perturbation between Na2 B1piu and alpha1sigmau+ states is considered.     

Resonant two-photon ionization spectroscopy of jet-cooled OsC

The optical spectrum of diatomic OsC has been investigated for the first time, with transitions recorded in the range from 17 390 to 22 990 cm(-1). Six bands were rotationally resolved and analyzed to obtain ground and excited state rotational constants and bond lengths. Spectra for six OsC isotopomers, 192 Os 12C (40.3% natural abundance), 190 Os 12C(26.0%), 189 Os 12C(16.0%), 188 Os 12C(13.1%), 187 Os 12C(1.9%), and 186 Os 12C(1.6%), were recorded and rotationally analyzed. The ground state was found to be X 3 Delta 3, deriving from the 4 delta 3 16 sigma 1 electronic configuration. Four bands were found to originate from the X 3 Delta 3 ground state, giving B 0"=0.533 492(33) cm(-1) and r 0 "=1.672 67(5) A for the 192 Os 12C isotopomer (1 sigma error limits); two of these, the 0-0[19.1]2<--X 3 Delta 3 and 1-0[19.1]2<--X 3 Delta 3 bands, form a vibrational progression with Delta G' 1/2=953.019 cm(-1). The remaining two bands were identified as originating from an Omega"=0 level that remains populated in the supersonic expansion. This level is assigned as the low-lying A 3 Sigma 0+ (-) state, which derives from the 4 delta 2 16 sigma 2 electronic configuration. The OsC molecule differs from the isovalent RuC molecule in having an X 3 Delta 3 ground state, rather than the X 2 delta 4, 1 Sigma+ ground state found in RuC. This difference in electronic structure is due to the relativistic stabilization of the 6s orbital in Os, an effect which favors occupation of the 6s-like 16 sigma orbital. The relativistic stabilization of the 16 sigma orbital also lowers the energy of the 4 delta 2 16 sigma 2, 3 Sigma(-) term, allowing this term to remain populated in the supersonically cooled molecular beam.     

Ab initio configuration interaction study of the low-lying 1Sigma+ electronic states of LiCl

Ab initio configuration interaction calculations have been performed for the X 1Sigma+ and B 1Sigma+ electronic states of LiCl. Potential energy curves, dipole moment functions, and dipole transition moments have been computed for internuclear distances between R = 2.5a0 and 50a0. Single- and double-excitation configuration interaction wave functions were constructed using molecular orbitals obtained from a two-state averaged multiconfiguration self-consistent-field calculation. This procedure yielded an accurate energy splitting between the covalent and ionic separated-atom limits. The calculated avoided crossing of the X and B state curves occurs at R = 16.2a0, in close agreement with previous calculations using a semiempirical covalent-ionic resonance model. X 1Sigma+ state spectroscopic constants are in excellent agreement with experimental values.     

Dynamic effects on the periselectivity, rate, isotope effects, and mechanism of cycloadditions of ketenes with cyclopentadiene

The cycloadditions of cyclopentadiene with diphenylketene and dichloroketene are studied by a combination of kinetic and product studies, kinetic isotope effects, standard theoretical calculations, and trajectory calculations. In contrast to recent reports, the reaction of cyclopentadiene with diphenylketene affords both [4 + 2] and [2 + 2] cycloadducts directly. This is surprising, since there is only one low-energy transition structure for adduct formation in mPW1K calculations, but quasiclassical trajectories started from this single transition structure afford both [4 + 2] and [2 + 2] products. The dichloroketene reaction is finely balanced between [4 + 2] and [2 + 2] cycloaddition modes in mPW1K calculations, as the minimum-energy path (MEP) leads to different products depending on the basis set. The MEP is misleading in predicting a single product, as trajectory studies for the dichloroketene reaction predict that both [4 + 2] and [2 + 2] products should be formed. The periselectivity does not reflect transition state orbital interactions. The (13)C isotope effects for the dichloroketene reaction are well-predicted from the mPW1K/6-31+G** transition structure. However, the isotope effects for the diphenylketene reaction are not predictable from the cycloaddition transition structure and transition state theory. The isotope effects also appear inconsistent with kinetic observations, but the trajectory studies evince that nonstatistical recrossing can reconcile the apparently contradictory observations. B3LYP calculations predict a shallow intermediate on the energy surface, but trajectory studies suggest that the differing B3LYP and mPW1K surfaces do not result in qualitatively differing mechanisms. Overall, an understanding of the products, rates, selectivities, isotope effects, and mechanism in these reactions requires the explicit consideration of dynamic trajectories.     

Modified transition state theory and negative apparent activation energies of simple metathesis reactions: application to the reaction CH3 + HBr --> CH4 + Br

A modified transition state theory (MTST) has been developed for gas-phase reactions with "negative barriers". The theory was applied to the reactions CH3 + HBr(DBr) --> CH4(CH3D) + Br (1a, 1b), which exhibit negative temperature dependences. Accurate ab initio calculations performed with coupled cluster theory extrapolated to the complete basis set limit revealed a transition state located at -2.3 kJ mol(-1) relative to the ground state of the reactants (in reaction 1a), as well as a shallow bound complex. The negative temperature dependence, the absolute values of the rate constant, and the isotope substitution effect are reproduced with good accuracy (10%), without any adjustment or fitting parameters. Analytical expressions are presented for MTST including angular momentum conservation, centrifugal barriers and tunneling. This analysis uses information about the possibly loose entrance barrier and the transition state but does not invoke a statistical intermediate complex.     

Calculations predict rapid tunneling by carbon from the vibrational ground state in the ring opening of cyclopropylcarbinyl radical at cryogenic temperatures

B3LYP/6-31G(d) calculations have been performed on the ring opening of cyclopropylcarbinyl radical 1 to 3-buten-1-yl radical 2. The dynamics of the reaction have been computed with canonical variational transition state theory (CVT), both with and without inclusion of small-curvature tunneling (SCT). The CVT + SCT calculations predict that 1 should undergo rapid and temperature-independent ring opening to 2 at cryogenic temperatures, by tunneling from the lowest vibrational level of 1.     

Excited state properties,fluorescence energies,and lifetimes of a poly(fluorene‐phenylene), based on TD‐DFT investigation

The structural and electronic properties of fluorene‐phenylene copolymer (FP)_n, n = 1–4 were studied by means of quantum chemical calculations based on density functional theory (DFT) and time dependent density functional theory (TD‐DFT) using B3LYP functional. Geometry optimizations of these oligomers were performed for the ground state and the lowest singlet excited state. It was found that (FP)_n is nonplanar in its ground state while the electronic excitations lead to planarity in its S₁ state. Absorption and fluorescence energies were calculated using TD‐B3LYP/SVP and TD‐B3LYP/SVP+ methods. Vertical excitation energies and fluorescence energies were obtained by extrapolating these values to infinite chain length, resulting in extrapolated values for vertical excitation energy of 2.89 and 2.87 eV, respectively. The S₁ ← S₀ electronic excitation is characterized as a highest occupied molecular orbital to lowest unoccupied molecular orbital transition and is distinguishing in terms of oscillator strength. Fluorescence energies of (FP)_n calculated from TD‐B3LYP/SVP and TD‐B3LYP/SVP+ methods are 2.27 and 2.26 eV, respectively. Radiative lifetimes are predicted to be 0.55 and 0.51 ns for TD‐B3LYP/SVP and TD‐B3LYP/SVP+ calculations, respectively. These fundamental information are valuable data in designing and making of promising materials for LED materials. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Optical observation of the 3s sigma gF3Pi u Rydberg state of N2

Using ultrahigh-resolution 1 XUV+1 UV two-photon ionization laser spectroscopy, the F (3)Pi(u)<--X (1)Sigma(g) (+)(0,0) transition of N(2) has been optically observed for the first time, and the 3s sigma(g)F (3)Pi(u)(upsilon=0) Rydberg level fully characterized with rotational resolution. The experimental spectroscopic parameters and predissociation level widths suggest strong interactions between the F state and the 3p pi(u)G (3)Pi(u) Rydberg and C(') (3)Pi(u) valence states, analogous to those well known in the case of the isoconfigurational (1)Pi(u) states.