Phosphine interacting with argon: potential energy surface and line widths of PH3 perturbed by Ar.

The phosphine-Ar (PH3-Ar) van der Waals complex's three-dimensional potential energy surface (3D-PES) was mapped along the intermonomer coordinates using the explicitly correlated Coupled Clusters approach. An analytical expansion of this 3D-PES is deduced. The complex characteristics of the intermolecular interactions between PH3 and Ar, which are at the origin of the pressure broadening of the PH3 rovibrational lines, are accurately described by this 3D-PES. Afterwards, the broadening of the phosphine lines perturbed by Ar at room temperature is computed using this 3D-PES. To be able to incorporate this 3D-PES into our collisional broadening computation software, we first modified it with a new "fractional" function. Then, we used the semiclassical Modified Robert and Bonamy model improved by the so-called notion of exact trajectory. For various branches of the ν2 and ν4 PH3 rovibrational bands, room temperature data are provided. Our data agree with the experimental measurements. The precise estimation of PH3 and Ar abundances in planetary atmosphere spectra should benefit greatly from the data provided here.

Selective adsorption of sulphur dioxide and hydrogen sulphide by metal-organic frameworks.

The removal of highly toxic gasses such as SO2 and H2S is important in various industrial and environmental applications. Metal organic frameworks (MOFs) are promising candidates for the capture of toxic gases owing to their favorable properties such as high selectivity, moisture stability, thermostability, acid gas resistance, high sorption capacity, and low-cost regenerability. In this study, we perform first principles density functional theory (DFT) and grand-canonical Monte Carlo (GCMC) simulations to investigate the capture of highly toxic gases, SO2 and H2S, by the recently designed ZTF and MAF-66 MOFs. Our results indicate that ZTF and MAF-66 show good adsorption performances for SO2 and H2S capture. The nature of the interactions between H2S or SO2 and the pore surface cavities was examined at the microscopic level. SO2 is adsorbed on the pore surface through two types of hydrogen bonds, either between O of SO2 with the closest H of the triazole 5-membred ring or between O of SO2 with the hydrogen of the amino group. For H2S inside the pores, the principal interactions between H2S and surface pores are due to a relatively strong hydrogen bonds established between the nitrogens of the organic part of MOFs and H2S. Also, we found that these interactions depend on the orientation of SO2/H2S inside the pores. Moreover, we have studied the influence of the presence of water and CO2 on H2S and SO2 capture by the ZTF MOF. The present GCMC simulations reveal that the addition of H2O molecules at low pressure leads to an enhancement of the H2S adsorption, in agreement with experimental findings. However, the presence of water molecules decreases the adsorption of SO2 irrespective of the pressure used. Besides, SO2 adsorption is increased in the presence of a small number of CO2 molecules, whereas the presence of carbon dioxide in ZTF pores has an unfavorable effect on the capture of H2S.

Fragmentation dynamics of CH3Clq+ (q = 2,3): theory and experiment.

A combined theoretical and experimental study of the dissociation of the di- and trication of the CH3Cl molecule has been performed. Experimentally, these multi-charged ions were produced after interactions of a CH3Cl effusive jet with a mono-energetic beam of H+ or Ar9+ projectile ions. Theoretically, we mapped the multi-dimensional potential energy surfaces of CH3Cl2+, H2CClH2+ and CH3Cl3+ species in their electronic ground and electronically excited states using post-Hartree-Fock configuration interaction methods. In addition to the obvious bond-breaking ionic fragments (i.e. H+ + CH2Cl+, H+ + CH2Cl2+ and CH3+ + Cl+), the formation of H2+ (+CHCl+ or CHCl2+), H3+ (+CCl+) and HCl+ (+CH2+) was observed upon bond rearrangement after ion impact of CH3Cl. The interaction strength of the incident projectiles is found to affect the relative yields on the observed dissociation channels, however, it has no effect on the kinetic energy releases of the fragmentation pathways. For the observed dissociation channels, plausible formation mechanisms were proposed. These reaction pathways take place on the ground and/or electronic excited potential energy surfaces of the doubly and triply charged CH3Cl ions, where spin-orbit and vibronic couplings are in action. Moreover, this work suggests that the mechanisms undertaken may depend on the multiply charged ion preparation by valence or inner-shell single photon photoionization, fast ion beam impact or ultrafast intense laser ionization.

Probing the dynamics of the photo-induced decarboxylation of neutral and ionic pyruvic acid.

The dynamics of the electronically excited pyruvic acid (PA) and of its unimolecular decomposition upon single photon ionisation are investigated by means of a table top fs laser and VUV synchrotron radiation. The latter is coupled with photo-ion/photo-electron coincidence acquisition devices that allow the identification of the ionic products coming from state-to-state fragmentation upon ionisation. The fs-based setup provides time-resolved mass spectra with 266 nm (= 4.661 eV) excitation and an 800 nm multiphoton probe. For interpretation, we carried out theoretical computations using a composite scheme combining density functional theory full molecular geometric optimisation and post-Hartree-Fock correction inclusion. We therefore determined the neutral and ionic species formed during these experiments and the corresponding dissociation channels. Although several PA isomers are found, we show that solely the most stable isomer of PA (i.e. Tc) is present in the molecular beam prior to ionisation. We determined its adiabatic ionisation energy (AIE = 10.031 ± 0.005 eV). The fragmentation of the Tc+ ion occurs at ∼0.4 eV above the threshold and it is dominated by the CC bond breaking channel, forming the HOCO fragment in conjunction with the CH3CO+ ion. The decarboxylation of Tc+ channels has a minor contribution, although they are more favourable thermodynamically. These findings are in contrast with the dominance of decarboxylation while fragmenting Tc populated in the S1-S3 states. For explanation, we invoke an indirect process populating first a short lived autoionising neutral state located in energy at the HOCO + CH3CO+ dissociation limit. Later on, fragmentation occurs, followed by autoionisation. On the other hand, the fs-based experiment does not reveal any appreciable dynamics for the Tc isomer of PA after a 266 nm excitation because of non-favourable Franck-Condon factors at this energy. In sum, our work highlights the importance of the couplings between the parent ion vibrational modes and the dissociative channels in the vicinity of the loss ionic fragmentation thresholds.

Theoretical treatment of IO-X (X = N2, CO, CO2, H2O) complexes.

Iodine monoxide (IO) is an important component of the biogeochemical cycle of iodine. For instance, it is present in the troposphere, where it plays a crucial role in the physical chemical processes involving iodine containing compounds. Here, we present a theoretical study on a series of atmospherically relevant complexes of IO with N2, CO, CO2 and H2O, where their structural and spectroscopic properties and their interaction energies are computed. Calculations are carried out by means of ab initio post Hartree-Fock (RCCSD(T) and RMP2) methods and density functional theory DFT (PBE0 and M05-2X) based approaches with and without the inclusion of dispersion correction. After comparison to RCCSD(T), we highlight the good performance of M05-2X(+D3) DFT in describing the bonding between IO and X (X = N2, CO, CO2, H2O). Moreover, we found that the IO-X (X = N2, CO, CO2, H2O) complexes are formed by non-covalent interactions between the two monomers. In sum, we characterized two types of complexes: I-bonded and O-bonded, where the former is more stable. The atmospheric implications of the present findings are also discussed such as in the formation of the iodine oxide particles (IOPs).

Threshold photoelectron spectroscopy of 9-methyladenine: theory and experiment.

We present a combined experimental and theoretical study of single-photon ionization of 9-methyladenine (9MA) in the gas phase. In addition to tautomerism, several rotamers due to the rotation of the methyl group may exist. Computations show, however, that solely one rotamer contributes because of low population in the molecular beam and/or unfavorable Franck-Condon factors upon ionization. Experimentally, we used VUV radiation available at the DESIRS beamline of the synchrotron radiation facility SOLEIL to record the threshold photoelectron spectrum of this molecule between 8 and 11 eV. This spectrum consists of a well-resolved band assigned mainly to vibronic levels of the D0 cationic state, plus a contribution from the D1 state, and two large bands corresponding to the D1, D2 and D3 electronically excited states. The adiabatic ionization energy of 9MA is measured at 8.097 ± 0.005 eV in close agreement with the computed value using the explicitly correlated coupled cluster approach including core valence, scalar relativistic and zero-point vibrational energy corrections. This work sheds light on the complex pattern of the lowest doublet electronic states of 9MA+. The comparison to canonical adenine reveals that methylation induces further electronic structure complication that may be important to understand the effects of ionizing radiation and the charge distribution in these biological entities at different time scales.

Identification of a Grotthuss proton hopping mechanism at protonated polyhedral oligomeric silsesquioxane (POSS) - water interface.

The attachment and dissociation of a proton from a water molecule and the proton transfers at solid-liquid interfaces play vital roles in numerous biological, chemical processes and for the development of sustainable functional materials for energy harvesting and conversion applications. Using first-principles computational methodologies, we investigated the protonated forms of polyhedral oligomeric silsesquioxane (POSS-H+) interacting with water clusters (Wn, where n = 1-6) as a model to quantify the proton conducting and localization ability at solid-liquid interfaces. Successive addition of explicit water molecules to POSS-H+ shows that the assistance of at least three water molecules is required to dissociate the proton from POSS with the formation of an Eigen cation (H9O4+), whereas the presence of a fourth water molecule highly favors the formation of a Zundel ion (H5O2+). Reaction pathway and energy barrier analysis reveal that the formation of the Eigen cation requires significantly higher energy than the Zundel features. This confirms that the Zundel ion is destabilized and promptly converts in to Eigen ion at this interface. Moreover, we identified a Grotthuss-type mechanism for the proton transfer through a water chain close to the interface, where symmetrical and unsymmetrical arrangements of water molecules around H+ of protonated POSS-H+ are involved in the conduction of proton through water wires where successive Eigen-to-Zundel and Zundel-to-Eigen transformations are observed in quick succession.

State selective fragmentation of doubly ionized sulphur dioxide.

Using multi-electron-ion coincidence measurements combined with high level calculations, we show that double ionisation of SO2 at 40.81 eV can be state selective. It leads to high energy products, in good yield, via a newly identified mechanism, which is likely to apply widely to multiple ionisation by almost all impact processes.

Explicitly correlated potential energy surface of the CH3Cl-He van der Waals complex and applications.

A new 3D-potential energy surface (3D-PES) for the weakly bound CH3Cl-He complex is mapped in Jacobi coordinates. Electronic structure calculations are performed using the explicitly correlated coupled clusters with single, double, and perturbative triple excitations approach in conjunction with the aug-cc-pVTZ basis set. Then, an analytical expansion of this 3D-PES is derived. This PES shows three minimal structures for collinear C-Cl-He arrangements and for He located in between two H atoms, in the plane parallel to the three H atoms, which is near the center of mass of CH3Cl. The latter form corresponds to the global minimum. Two maxima are also found, which connect the minimal structures. We then evaluated the pressure broadening coefficients of the spectral lines of CH3Cl in a helium bath based on our ab initio potential. Satisfactory agreement with experiments was observed, confirming the good accuracy of our 3D-PES. We also derived the bound rovibronic levels for ortho- and para-CH3Cl-He dimers after quantum treatment of the nuclear motions. For both clusters, computations show that although the ground vibrational state is located well above the intramolecular isomerization barriers, the rovibronic levels may be associated with a specific minimal structure. This can be explained by vibrational localization and vibrational memory effects.

In silico design of a new Zn-triazole based metal-organic framework for CO2 and H2O adsorption.

In search for future good adsorbents for CO2 capture, a nitrogen-rich triazole-type Metal-Organic Framework (MOF) is proposed based on the rational design and theoretical molecular simulations. The structure of the proposed MOF, named Zinc Triazolate based Framework (ZTF), is obtained by replacing the amine-organic linker of MAF-66 by a triazole, and its structural parameters are deduced. We used grand-canonical Monte Carlo (GCMC) simulations based on generic classical force fields to correctly predict the adsorption isotherms of CO2 and H2O. For water adsorption in MAF-66 and ZTF, simulations revealed that the strong hydrogen bonding interactions of water with the N atoms of triazole rings of the frameworks are the main driving forces for the high adsorption uptake of water. We also show that the proposed ZTF porous material exhibits exceptional high CO2 uptake capacity at low pressure, better than MAF-66. Moreover, the nature of the interactions between CO2 and the MAF-66 and ZTF surface cavities was examined at the microscopic level. Computations show that the interactions occur at two different sites, consisting of Lewis acid-Lewis base interactions and hydrogen bonding, together with obvious electrostatic interactions. In addition, we investigated the influence of the presence of H2O molecules on the CO2 adsorption on the ZTF MOF. GCMC simulations reveal that the addition of H2O molecules leads to an enhancement of the CO2 adsorption at very low pressures but a reduction of this CO2 adsorption at higher pressures.

Carbazole derivatives containing chalcone analogues targeting topoisomerase II inhibition: First principles characterization and QSAR modelling.

Recently, a series of carbazole derivatives containing chalcone analogues (CDCAs) were synthetized as potent anticancer agents and apoptosis inducers. These compounds target the inhibition of topoisomerase II and present cytotoxic activities. After comparison to experiment, we validated the use of B3LYP, a density functional theory-based approach, to describe the structure and molecular properties of the carbazole subunit and CDCAs compounds of interest. Then, we derived relationships between the chemical descriptors and activity of these carbazole derivatives using multi-parameter optimization and quantitative structure activity relationships (QSAR) approaches. For the QSAR studies, we used multiple linear regression and artificial neural network statistical modelling. Our predicted activities are in good agreement with the experimental ones. We found that the most important parameter influencing the activity of the considered compounds is the octanol-water partition coefficient, highlighting the importance of flexibility as a key molecular parameter to favor cell membrane crossing and enhance the action of these CDCAs against topoisomerase II. Our results provide useful guidelines for designing new oral active CDCAs medicaments for cytotoxic inhibition.

IO(X2Π)-Ar cluster: ab initio potential energy surface and dynamical computations.

Iodine oxide (IO) is an important tropospheric molecule. In the present paper, we mapped the potential energy surfaces (PESs) of the doubly degenerate IO(X2Π)-Ar van der Waals system using single- and double-excitation coupled cluster approaches with non-iterative perturbation treatment of triple excitations [RCCSD(T)] extrapolated to the complete basis set (CBS) limit. In addition to bent local minima, we identified a linear Ar-IO complex as a global minimum. Afterwards, we performed scattering calculations on these PESs, considering the non-zero spin-orbit contribution and the Renner-Teller effect. The integral cross-sections exhibit an oscillatory structure vs. the final rotational state, as already observed for the NO(X2Π)-Ar system. Moreover, computations reveal that the Ar-IO complex is stable toward dissociation into IO and Ar. Therefore, it can be found in the atmosphere and participates in iodine compound physical chemical processes occurring there.

Single photon ionization of methyl isocyanide and the subsequent unimolecular decomposition of its cation: experiment and theory.

Methyl isocyanide, CH3NC, is a key compound in astrochemistry and astrobiology. A combined theoretical and experimental investigation of the single photon ionization of gas phase methyl isocyanide and its fragmentation pathways is presented. Vacuum ultraviolet (VUV) synchrotron radiation based experiments are used to measure the threshold photoelectron photoion coincidence (TPEPICO) spectra between 10.6 and 15.5 eV. This allowed us to experimentally determine the adiabatic ionization energy (AIE) and fragment ion appearance energies (AE) of gas-phase methyl isocyanide. Its AIE has been measured with a precision never achieved before. It is found to be AIEexp = 11.263 ± 0.005 eV. We observe a vibrational progression upon ionization corresponding to the population of vibrational levels of the ground state of the methyl isocyanide cation. In addition, four fragment ion appearance energies (AEs) were measured to be AE (m/z 40) = 12.80 ± 0.05 eV, AE (m/z 39) = 13.70 ± 0.05, AE (m/z 15) = 13.90 ± 0.05 eV, AE (m/z 14) 13.85 ± 0.05 eV, respectively. In order to interpret the experimental data, we performed state-of-the-art computations using the explicitly correlated coupled cluster approach. We also considered the zero-point vibrational energy (ZPVE), core-valence (CV) and scalar relativistic (SR) effects. The results of theoretical calculations of the AIE and AEs are in excellent agreement with the experimental findings allowing for assignment of the fragmentations to the loss of neutral H, H2, CN and HCN upon ionization of CH3NC. The computations show that in addition to the obvious bond breakings, some of the corresponding ionic fragments result from rearrangements - upon photon absorption - either before or after electron ejection.

Gold with +4 oxidation state compounds: mass spectrometric and theoretical characterization of AuO2.

Using an ab initio methodology and mass spectrometric study we identify AuO2+ as a metastable species in the gas phase. This represents the first characterization of a gas phase compound of gold with the oxidation state +4. Computations show that this dication exhibits deep potential wells with long lived electronic states. Its electronic ground state is of 4∑- symmetry, which is known for very few molecular ground states. We also discussed the O + Au2+ collision dynamics, which leads mostly to charge transfer to form Au+ and O+ species. This identification may help in identifying new routes for the reactivity of gold in the gas phase, in solution and in the condensed phase.

Spectroscopy and characterization of AlNX (X = O and S): Triatomic circumstellar molecules.

Three isomers of the triatomic [Al, N, O] molecular system have been observed in a solid argon matrix by infrared absorption spectroscopy using 15N and 18O isotopic substitution. The present work provides high-level quantum chemical predictions of their spectroscopic parameters to observe this system in the interstellar medium. The spectroscopic parameters, stability, and geometries of the lowest stable isomers of its isoelectronic system [Al, N, S] were characterized using coupled-cluster CCSD(T), explicitly correlated coupled-cluster CCSD(T)-F12, and multireference configuration interaction. The three-dimensional potential energy surfaces of all isomers were computed at the CCSD(T)-F12/aug-cc-pV5Z level, and a set of spectroscopic parameters were calculated. In both systems, the most stable isomer is linear with an X3Σ- electronic ground state, and all linear isomers are characterized by small bending modes of less than 200 cm-1. Due to their large dipole moments, the high intensities of such modes, and the nonexistence of anharmonic resonance complicating their spectra, our results facilitate the detection of AlNO and AlNS in the laboratory or in the interstellar medium.

Copper-Chalcogen Bonds in Olfaction: Accurate ab Initio Characterization of CuSH and CuOH.

From highly correlated ab initio methods at the CCSD(T) level, with and without the inclusion of scalar relativistic effects, accurate 3D potential energy surfaces (PESs) of CuSH and CuOH were generated in their electronic ground state. The PESs are incorporated into perturbative and variational treatments of nuclear motions. Using these approaches, we derived a set of accurate spectroscopic parameters and the pattern of the vibrational states of CuXH (X = O,S) up to 4000 cm-1. The applied calculations at the CCSD(T)/aug-cc-pV5Z-DK level of theory are validated using several experimental high-resolution spectroscopy data (including rotational spectroscopy) available in the literature. The optimized equilibrium geometries of CuSH and CuOH with bending angles of 93.9° and 110.2°, Cu-X bond lengths of 2.088 and 1.764 Å, and X-H bond lengths of 1.344 and 0.961 Å, respectively, accurately reproduce the experimental structures and clearly show the importance of the scalar relativistic effects. The anharmonic frequencies, ν1, ν2, and ν3, are computed at 3655.5, 746.3, and 623.3 cm-1 for CuOH and at 2572.9, 588.9, and 396.6 cm-1 for CuSH, respectively. Finally, the PESs are derived as anharmonic force fields for CuXH (X = O, S) that can be incorporated into large scale molecular dynamics simulations of Cu-X containing compounds. The results are discussed within the scope of available literature on the effects of substitution of oxygen by sulfur for putative molecular recognition mechanisms.

Spectroscopy and Stability of AlOP: A Possible Progenitor of Interstellar Metal.

Standard and explicitly correlated coupled-cluster theory computations in conjunction with large basis sets are performed to characterize [Al,P,O] isomers. Three isomers, namely, linear-AlOP, bent-AlOP, and linear-OAlP, are found to be stable species. Their optimized equilibrium geometries, harmonic vibrational frequencies, rotational constants, and relative energies are deduced. In addition, a set of spectroscopic parameters is generated from the three-dimensional potential energy surfaces of each isomer at the (R)CCSD(T)/aug-cc-pV5Z level. The linear isomers have an X3Σ- electronic ground state and are characterized as weakly bound systems or floppy molecules due to their low-frequency bending modes (<150 cm-1). The dipole moment of linear-AlOP is calculated to be 1.48 D. By comparison, a much larger dipole moment is computed for linear-OAlP (5.01 D), indicating lower ionic character in AlOP. Both the linear-OAlP and linear-AlOP isomers are suggested to be good candidates for detection in interstellar media by radio astronomy.

Spectroscopy of the electronic excited states of thioxophosphane, HPS, and of its deuterated species.

The stable low energy states of the HPS and DPS molecules have been studied through multi-reference ab initio methods in conjunction with large atomic basis sets. Stable states for these species have been examined up to 7 eV above the ground state minimum. We found six stable electronic states that are mostly mono-configurational. These states may be involved in the photodynamics and photodissociation of this molecule. In particular, the 2 1A' state presents two minima on the potential energy surface, one of them close to linear configuration. This state may be populated after the absorption of a visible photon from the ground state and gives rise to large amplitude motions that may eventually induce isomerization to electronically excited HSP. Moreover, we characterized these states spectroscopically to facilitate the assignment of the vibronic spectra of the HPS and DPS species. For these low-energy states, we thus computed vertical and adiabatic excitation energies, and for the stable ones, a full set of spectroscopic constants including harmonic frequencies and anharmonic vibrational, rotational, and centrifugal distortion constants. The calculated potential energy surfaces for these states have been used in a variational procedure to deduce the pattern of vibrational levels up to 4000 cm-1 above the corresponding vibrationless level. Our data may serve for the assignment of the IR and Vis spectra of HPS and DPS.

Disentangling the complex spectrum of the ethynyl cation.

The ethynyl cation, C2H+, is of great importance in astrophysical media and in combustion. It is involved in the formation of larger organic compounds and in their decomposition mechanisms. Here, we investigate the low-lying electronic states of this cation using pure ab initio methodologies. The evolution of its potential energy surfaces along the stretching and bending coordinates reveals a high density of electronic states that favours mutual interactions and the mixing of wavefunctions. The ground state is of 3Π space symmetry and the lowest singlet state (1Π) is found to be a quasi-linear-quasi-linear Renner-Teller system. Our work suggests that the (spin-)rovibronic spectrum of such a molecular system is complicated, because of the contributions of multiple couplings, including Renner-Teller, vibronic and spin-orbit. We also deduced the adiabatic ionization energy of the ethynyl radical, in good agreement with recent measurements. In summary, our work shows that the ethynyl cation, in spite of its small size, still represents a challenging molecular problem to be solved.

Rotational (de-)excitation of isocyanogen by collision with helium at low energies.

Isocyanogen, CNCN, was discovered very recently in the interstellar medium (ISM). At present, the rate coefficients for the rotational (de-)excitation of CNCN by collisions with He are determined. First, we mapped the interaction potential between CNCN and He in Jacobi coordinates using highly correlated ab initio methodology. Then, an analytical expansion of the CNCN-He potential energy surface is derived. Later on, quantum dynamical treatments of nuclear motions are performed using the close coupling technique. We obtained the cross sections for the rotational (de-)excitation of CNCN after a collision by He up to 2000 cm-1 total energies. These cross sections are used to deduce the collision rates in the 10-300 K range. These data are needed for modeling the CNCN abundances in the ISM. This work should help for determining the abundance of such non-symmetrical dicyanopolyynes in astrophysical media and indirectly the symmetric one [Cyanogen (NCCN)].