Photodissociation of the CH3O and CH3S radical molecules: an ab initio electronic structure study.

The electronic states and the spin-orbit couplings between them involved in the photodissociation process of the radical molecules CH3X, CH3X → CH3 + X (X = O, S), taking place after the Ã(2A1) ← X[combining tilde](2E) transition, have been investigated using highly correlated ab initio techniques. A two-dimensional representation of both the potential-energy surfaces (PESs) and the couplings is generated. This description includes the C-X dissociative mode and the CH3 umbrella mode. Spin-orbit effects are found to play a relevant role in the shape of the excited state potential-energy surfaces, particularly in the CH3S case where the spin-orbit couplings are more than twice more intense than in CH3O. The potential surfaces and couplings reported here for the present set of electronic states allow for the first complete description of the above photodissociation process. The different photodissociation mechanisms are analyzed and discussed in light of the results obtained.

Rotational Excitation of the CP(Χ2Σ+) Open Shell Molecule Due to Collision with He(1S).

Phosphorus bearing molecules have been discovered in the circumstellar and interstellar media. Modeling their abundance accurately requires computations of rate coefficients induced by collision with He and H2 (i.e., the most abundant gaseous components). These calculations may be carried out by first determining highly accurate potential energy surface (PES) and cross sections. In this paper, we present the first PES of the CP(X2Σ+)-He(1S) van der Waals collisional complex. The ab initio interaction potential was performed using the explicitly correlated restricted coupled cluster approach with simple, double, and perturbative triple excitation (RCCSD(T)-F12) in connection with the augmented-correlation consistent-polarized valence triple-ζ Gaussian basis set (aug-cc-pVTZ). The potential presents two minima of -18.62 cm-1 and -18.72 cm-1. From the PES obtained, we have computed state-to-state excitation cross sections of CP due to collision with He for energies up to 500 cm-1. Rotational transitions involving the fine-structure levels of the CP molecule were treated with a recoupling technique based on the scattering matrix calculated with the exact quantum mechanical close coupling method. Discussions on the propensity rules between the fine-structure levels were made and we found that the Δj = ΔN transitions are favored with respect to the Δj ≠ ΔN ones. The data presented in this paper may have a great impact on the accurate determination of the CP abundance in space.

Periodic Dispersion-Corrected Approach for Isolation Spectroscopy of N2 in an Argon Environment: Clusters, Surfaces, and Matrices.

Ab initio and Perdew, Burke, and Ernzerhof (PBE) density functional theory with dispersion correction (PBE-D3) calculations are performed to study N2-Arn (n ≤ 3) complexes and N2 trapped in Ar matrix (i.e., N2@Ar). For cluster computations, we used both Møller-Plesset (MP2) and PBE-D3 methods. For N2@Ar, we used a periodic-dispersion corrected model for Ar matrix, which consists on a slab of four layers of Ar atoms. We determined the equilibrium structures and binding energies of N2 interacting with these entities. We also deduced the N2 vibrational frequency shifts caused by clustering or embedding compared to an isolated N2 molecule. Upon complexation or embedding, the vibrational frequency of N2 is slightly shifted, while its equilibrium distance remains unchanged. This is due to the weak interactions between N2 and Ar within these compounds. Our calculations show the importance of inclusion of dispersion effects for the accurate description of geometrical and spectroscopic parameters of N2 isolated, in interaction with Ar surfaces, or trapped in Ar matrices.

New insights into the photoswitching mechanisms of normal dithienylethenes.

The photoswitching and competitive processes of the referent photochromic diarylethene derivative 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene (DTE) and a novel bridged analog DTE-m5 have been investigated by state-of-the-art TD-DFT calculations and ultrafast spectroscopy supported by advanced chemometric data treatments. Focusing on DTE, the overall deactivation pathway of both antiparallel (AP) and parallel (P) conformers of the open form (OF) (1 : 1 in solution) has been resolved and rationalized starting from the Franck-Condon (FC) region to the ground state recovery. For the photo-excited P conformer, after ultrafast relaxation (∼200 fs) towards the S1 relaxed state, an expected ISC occurred (55 ps) to produce a triplet state, 3P, the latter relaxing within 2.5 µs. Concerning the AP conformer, the photocyclization reaction is reported to proceed immediately (100 fs) starting from the FC region while the relaxed singlet state is populated in parallel. For the first time, we discovered that the latter state evolves through an unexpected ISC process (1 ps) giving rise to a second triplet state,3AP. For DTE-m5, by slightly constraining the molecule with the bridge, this triplet becomes reactive and participates in the formation of 10% of closed form (CF) probably through an adiabatic mechanism. Concerning the photoreversion, in accordance with the literature, we report on a two-step process, a 190 fs vibrational relaxation followed by a 6 ps ring-opening reaction. For the overall species at the singlet or triplet manifold, the use of advanced MCR-ALS allows us to obtain specific spectral signatures. This study is therefore a new step within the comprehension of DTE photochemistry.

Weak intramolecular interaction effects on the torsional spectra of ethylene glycol, an astrophysical species.

An elaborate variational procedure of reduced dimensionality based on explicitly correlated coupled clusters calculations is applied to understand the far infrared spectrum of ethylene-glycol, an astrophysical species. This molecule can be classified in the double molecular symmetry group G8 and displays nine stable conformers, gauche and trans. In the gauche region, the effect of the potential energy surface anisotropy due to the formation of intramolecular hydrogen bonds is relevant. For the primary conformer, stabilized by a hydrogen bond, the ground vibrational state rotational constants are computed to be A0 = 15 369.57 MHz, B0 = 5579.87 MHz, and C0 = 4610.02 MHz corresponding to differences of 6.3 MHz, 7.2 MHz, and 3.5 MHz from the experimental parameters. Ethylene glycol displays very low torsional energy levels whose classification is not straightforward and requires a detailed analysis of the torsional wavefunctions. Tunneling splittings are significant and unpredictable due to the anisotropy of the potential energy surface PES. The ground vibrational state splits into 16 sublevels separated ∼142 cm(-1). The splitting of the "G1 sublevels" was calculated to be ∼0.26 cm(-1) in very good agreement with the experimental data (0.2 cm(-1) = 6.95 MHz). Transitions corresponding to the three internal rotation modes allow assignment of previously observed Q branches. Band patterns, calculated between 362.3 cm(-1) and 375.2 cm(-1), 504 cm(-1) and 517 cm(-1), and 223.3 cm(-1) and 224.1 cm(-1), that correspond to the tunnelling components of the v21 fundamental (v21 = OH-torsional mode), are assigned to the prominent experimental Q branches.

Structure, Reactivity, and Fragmentation of Small Multi-Charged Methane Clusters.

Small methane clusters (CH4)n are irradiated using intense femtosecond laser excitation at 624 nm. The ionized species and those resulting from their fragmentation are detected via time-of-flight mass spectrometry (TOF MS). We find evidence of bound, multiply charged methane molecules and clusters resulting from Coulomb explosion upon exposure to highly energetic, ultrafast radiation. The assignment of the mass spectra is done after first-principles calculations (at the (R)MP2/aug-cc-pVXZ (X = D,T) level) on the charged (CH4)n(q+) clusters (n = 1-4, q = 1-4). We also considered the cluster stabilities and fragments that may result from intracluster molecular reactivity. Complex intracluster ion-molecule reactions induced by photoionization are expected to occur. Interestingly, we show that multi charged small methane clusters undergo intracluster reactions and fragmentations which are different from those observed for isolated methane ions or for large ionized methane clusters.

Stereoisomers of hydroxymethanes: Probing structural and spectroscopic features upon substitution.

Ab initio studies on CHx(OH)4-x (x = 0-3) polyols are carried out to derive their structural and spectroscopic features. Several stereoisomers (both equilibrium structures and transition states) are found. Some are predicted here for the first time. We determined hence their geometrical parameters, vibrational frequencies, electronic excitation energies for the singlet manifold, and IR spectra. While the IR spectra for all polyols present similar shapes, their UV spectra exhibit however distinct band origin that are specific to each polyol and more interestingly to each diasteroisomer. Stereoelectronic effects are also noticed and discussed. It is suggested that UV spectroscopy is an efficient probe to experimentally identify polyols in mixtures involving polyols.

Rotational Excitation of the OH(+) Radical by Collision with H at Low Temperature.

A ro-vibrationally inelastic close coupling study of the rotational excitation of OH(+)(X(3)Σ(-)) by collisions with H((2)S) is presented. The two lowest potential energy surfaces of doublet and quadruplet spin multiplicity are involved. The former is the one we developed recently, and the latter is a modified version of the quadruplet surface of Martinez et al. to include the long-range charge-induced-dipole potential. The details of the modification of this surface are presented as well as the comparison of the rotational excitation resulting from collisions with hydrogen on these two surfaces. The effect of the coupling between vibration and rotation on the rotational excitation rate is also discussed, as the potential well depth of the doublet surface is quite large and allows the coupling between many vibrational channels of OH(+). As the hydrogen exchange reaction can occur for both potential energy surfaces, we discuss the reliability of the approximation made by the calculation of the cross sections with a quantum dynamics limited to the inelastic process. The relative importance of the collisions on the doublet or quadruplet surface within a given rotational transition is also discussed.

Characterization and reactivity of the weakly bound complexes of the [H, N, S](-) anionic system with astrophysical and biological implications.

We investigate the lowest electronic states of doublet and quartet spin multiplicity states of HNS(-) and HSN(-) together with their parent neutral triatomic molecules. Computations were performed using highly accurate ab initio methods with a large basis set. One-dimensional cuts of the full-dimensional potential energy surfaces (PESs) along the interatomic distances and bending angle are presented for each isomer. Results show that the ground anionic states are stable with respect to the electron detachment process and that the long range parts of the PESs correlating to the SH(-) + N, SN(-) + H, SN + H(-), NH + S(-), and NH(-) + S are bound. In addition, we predict the existence of long-lived weakly bound anionic complexes that can be formed after cold collisions between SN(-) and H or SH(-) and N. The implications for the reactivity of these species are discussed; specifically, it is shown that the reactions involving SH(-), SN(-), and NH(-) lead either to the formation of HNS(-) or HSN(-) in their electronic ground states or to autodetachment processes. Thus, providing an explanation for why the anions, SH(-), SN(-), and NH(-), have limiting detectability in astrophysical media despite the observation of their corresponding neutral species. In a biological context, we suggest that HSN(-) and HNS(-) should be incorporated into H2S-assisted heme-catalyzed reduction mechanism of nitrites in vivo.

Understanding of matrix embedding: a theoretical spectroscopic study of CO interacting with Ar clusters, surfaces and matrices.

Through benchmark studies, we explore the performance of PBE density functional theory, with and without Grimme's dispersion correction (DFT-D3), in predicting spectroscopic properties for molecules interacting with rare gas matrices. Here, a periodic-dispersion corrected model of matrix embedding is used for the first time. We use PBE-D3 to determine the equilibrium structures and harmonic vibrational frequencies of carbon monoxide in interaction with small Ar clusters (CO-Arn, n = 1, 2, 3), with an Ar surface and embedded in an Ar matrix. Our results show a converging trend for both the vibrational frequencies and binding energies when going from the gas-phase to a fully periodic approach describing CO embedding in Ar. This trend is explained in terms of solvation effects, as CO is expected to alter the structure of the Ar matrix. Due to a competition between CO-Ar interactions and Ar-Ar interactions, perturbations caused by the presence of CO are found to extend over several Šin the matrix. Accordingly, it is mandatory to fully relax rare gas matrices when studying their interaction with embedded molecules. Moreover, we show that the binding energy per Ar is almost constant (∼-130 cm(-1) atom(-1)) regardless of the environment of the CO molecule. Finally, we show that the concentration of the solute into the cold matrix influences the spectroscopic parameters of molecules embedded into cold matrices. We suggest hence that several cautions should be taken before comparing these parameters to gas phase measurements and to theoretical data of isolated species.

Theoretical characterization of dimethyl carbonate at low temperatures.

Highly correlated ab initio methods (CCSD(T) and RCCSD(T)-F12) are employed for the spectroscopic characterization of the gas phase of dimethyl carbonate (DMC) at low temperatures. DMC, a relevant molecule for atmospheric and astrochemical studies, shows only two conformers, cis-cis and trans-cis, respectively, of C2v and Cs symmetries. cis-cis-DMC represents the most stable form. Using RCCSD(T)-F12 theory, the two sets of equilibrium rotational constants have been computed to be Ae = 10 493.15 MHz, Be = 2399.22 MHz, and Ce = 2001.78 MHz (cis-cis) and to be Ae = 6585.16 MHz, Be = 3009.04 MHz, and Ce = 2120.36 MHz (trans-cis). Centrifugal distortions constants and anharmonic frequencies for all of the vibrational modes are provided. Fermi displacements are predicted. The minimum energy pathway for the cis-cis → trans-cis interconversion process is restricted by a barrier of ∼3500 cm(-1). DMC displays internal rotation of two methyl groups. If the nonrigidity is considered, the molecule can be classified in the G36 (cis-cis) and the G18 (trans-cis) symmetry groups. For cis-cis-DMC, both internal tops are equivalent, and the torsional motions are restricted by V3 potential energy barriers of 384.7 cm(-1). trans-cis-DMC shows two different V3 barriers of 631.53 and 382.6 cm(-1). The far-infrared spectra linked to the torsional motion of both conformers are analyzed independently using a variational procedure and a two-dimensional flexible model. In cis-cis-DMC, the ground vibrational state splits into nine components: one nondegenerate, 0.000 cm(-1) (A1), four quadruply degenerate, 0.012 cm(-1) (G), and four doubly degenerate 0.024 cm(-1) (E1 and E3). The methyl torsional fundamentals are obtained to lie at 140.274 cm(-1) (ν15) and 132.564 cm(-1) (ν30).

Theoretical spectroscopic characterization of the ArBeO complex.

Using the recently developed explicitly correlated coupled cluster method in connection with the aug-cc-pVTZ basis set, we generated the three-dimensional potential energy surface (3D-PES) of the ground state of the Ar-BeO complex. This PES covers the regions of the global and local minima, the saddle point, and the dissociation of the complex. The PES is also used for the calculation of the rovibrational spectrum up to the dissociation limit. The high density of levels which is observed favors the mixing of the states and hence the occurrence of anharmonic resonances. The wavefunctions of the high rovibrational levels exhibit large amplitude motions in addition to strong anharmonic resonances. Our theoretical spectrum should be helpful in identifying the van der Waals modes of this complex in laboratory.

Theoretical spectroscopic investigations of HNS(q) and HSN(q) (q = 0, +1, -1) in the gas phase.

We performed accurate ab initio investigations of the geometric parameters and the vibrational structure of neutral HNS/HSN triatomics and their singly charged anions and cations. We used standard and explicitly correlated coupled cluster approaches in connection with large basis sets. At the highest levels of description, we show that results nicely approach those obtained at the complete basis set limit. Moreover, we generated the three-dimensional potential energy surfaces (3D PESs) for these molecular entities at the coupled cluster level with singles and doubles and a perturbative treatment of triple excitations, along with a basis set of augmented quintuple-zeta quality (aug-cc-pV5Z). A full set of spectroscopic constants are deduced from these potentials by applying perturbation theory. In addition, these 3D PESs are incorporated into variational treatment of the nuclear motions. The pattern of the lowest vibrational levels and corresponding wavefunctions, up to around 4000 cm(-1) above the corresponding potential energy minimum, is presented for the first time.

Quantum dynamical study of the O((1)D) + CH4 → CH3 + OH atmospheric reaction.

Time independent quantum mechanical (TIQM) scattering calculations have been carried out for the O((1)D) + CH4(X(1)A1) → CH3(X(2)A2″) + OH(X(2)Π) atmospheric reaction, using an ab initio ground potential energy surface where the CH3 group is described as a pseudo-atom. Total and state-to-state reaction probabilities for a total angular momentum J = 0 have been determined for collision energies up to 0.5 eV. The vibrational and rotational state OH product distributions show no specific behavior. The rate coefficient has been calculated by means of the J-shifting approach in the 10-500 K temperature range and slightly depends on T at ordinary temperatures (as expected for a barrierless reaction). Quantum effects do not influence the vibrational populations and rate coefficient in an important way, and a rather good agreement has been found between the TIQM results and the quasiclassical trajectory and experimental ones. This reinforces somewhat the reliability of the pseudo-triatomic approach under the reaction conditions explored.

Accurate global potential energy surface for the H + OH+ collision.

We mapped the global three-dimensional potential energy surface (3D-PES) of the water cation at the MRCI/aug-cc-pV5Z including the basis set superposition (BSSE) correction. This PES covers the molecular region and the long ranges close to the H + OH(+)(X(3)Σ(-)), the O + H2(+)(X(2)Σg(+)), and the hydrogen exchange channels. The quality of the PES is checked after comparison to previous experimental and theoretical results of the spectroscopic constants of H2O(+)(X(2)B1) and of the diatomic fragments, the vibronic spectrum, the dissociation energy, and the barrier to linearity for H2O(+)(X(2)B1). Our data nicely approach those measured and computed previously. The long range parts reproduce quite well the diatomic potentials. In whole, a good agreement is found, which validates our 3D-PES.

Electronic structure of the [MgO3]+ cation.

Accurate ab initio calculations are performed to investigate the stable isomers of [MgO(3)](+) and its lowest electronic states at both molecular and asymptotic regions. The calculations are done using large basis sets and configuration interaction methods including the complete active space self-consistent field, the internally contracted multi-reference configuration interaction, the standard coupled cluster (RCCSD(T)) approaches and the newly implemented explicitly correlated coupled cluster method (RCCSD(T)-F12). The presence of three stable forms is predicted: a cyclic global minimum c-MgO(3)(+), which is followed by a quasi-linear isomer, l2-MgO(3)(+). A third isomer of C(s) symmetry (l1-MgO(3)(+)) is also found. Moreover, we computed the one-dimensional cuts of the six-dimensional potential energy surfaces of the lowest doublet and quartet electronic states of [MgO(3)](+) along the R(MgO) and R(OO) stretching coordinates covering both the molecular and the asymptotic regions. These curves are used later for discussing the metastability of this cation and to propose plausible mechanisms for the Mg(+) + O(3) atmospherically important ion-molecule reaction and related reactive channels.

Quantitative analysis of pathological nails using laser-induced breakdown spectroscopy (LIBS) technique.

Laser-induced breakdown spectroscopy (LIBS) has been used as a potential method for simultaneous measurement of the elements Ca, Na, and K, for normal and pathological nails. We compared the measured LIBS spectra of these elements for normal and pathological nails. The B²∑+ --> X²∑+ violet band emission spectrum of CN was used for the estimation of the transient temperature of the plasma plume and consequently of the sample surface considering thermodynamic equilibrium.

Electronic states of MgO: Spectroscopy, predissociation, and cold atomic Mg and O production.

We used multiconfigurational methods and a large basis set to compute the potential energy curves of the valence and valence-Rydberg electronic states of MgO molecule. New bound electronic states are found. Using these highly correlated wave functions, we evaluated their mutual spin-orbit couplings and transition moment integrals. For the bound electronic states of MgO, we deduced an accurate set of spectroscopic constants that agree remarkably well with experimental results. Moreover, our potentials, transition moments, and spin-orbit coupling evolutions are incorporated into Fermi golden rule calculations to deduce the radiative lifetimes of MgO(B (1)Σ(+)) rovibrational levels and the natural lifetimes of MgO(A (1)Π) vibrational levels, where a good agreement is found with experimental values. Finally, we suggest new routes for the production of cold Mg and O atoms and cold MgO molecules.

Rotational excitation and de-excitation of C(2)(X 1Sigma(g)+) by para-H(2)(j = 0).

For the van der Waals C(2)(X (1)Sigma(g)(+))-H(2) molecular system, we generated a new ab initio potential energy surface (PES). We mapped this PES at the multireference internally contracted configuration-interaction method including the Davidson correction together with a large diffuse basis set. Then, we incorporated our PES into quantum scattering calculations at the close coupling and infinite order sudden approximation methods to cover collision energies ranging from 0.1 up to 4000 cm(-1). After Boltzmann thermal averaging, rate coefficients for temperatures of up to 1000 K are deduced. Discrepancies between our new rates and those computed previously are noticed. This should induce deviations in astrophysical modeling.

Rotationally inelastic collisions of methinoposphide (HCP) with para-H(2) at low temperature.

The interaction potential energy surface of the methinoposphide (HCP)-H(2) complex is calculated at the ab initio coupled-cluster level of theory with an aug-cc-pVTZ Gaussian basis set. The [H-C] and [C-P] bond lengths of HCP are set to their values at the linear equilibrium ground vibrational level of the molecule. The calculated interaction energy presents two minima located 106.3 and 67.6 cm(-1) below the HCP+H(2) dissociation limit. Using the interaction potential obtained, we have computed collision excitation cross sections in the close-coupling approach and downward rate coefficients at low temperature, i.e., T