Direct determination of the ionization energies of PtC, PtO, and PtO2 with VUV radiation

Photoionization efficiency curves were measured for gas-phase PtC, PtO, and PtO2 using tunable vacuum ultraviolet (VUV) radiation at the Advanced Light Source. The molecules were prepared by laser ablation of a platinum tube, followed by reaction with CH4 or N2O and supersonic expansion. These measurements provide the first directly measured ionization energy for PtC, IE(PtC) = 9.45 +/- 0.05 eV. The direct measurement also gives greatly improved ionization energies for the platinum oxides, IE(PtO) = 10.0 +/- 0.1 eV and IE(PtO2) = 11.35 +/- 0.05 eV. The ionization energy connects the dissociation energies of the neutral and cation, leading to greatly improved 0 K bond dissociation energies for the neutrals: D0(Pt-C) = 5.95 +/- 0.07 eV, D0(Pt-O) = 4.30 +/- 0.12 eV, and D0(OPt-O) = 4.41 +/- 0.13 eV, as well as enthalpies of formation for the gas-phase molecules DeltaH(0)(f,0)(PtC(g)) = 701 +/- 7 kJ/mol, DeltaH(0)(f,0)(PtO(g)) = 396 +/- 12 kJ/mol, and DeltaH(0)(f,0)(PtO2(g)) = 218 +/- 11 kJ/mol. Much of the error in previous Knudsen cell measurements of platinum oxide bond dissociation energies is due to the use of thermodynamic second law extrapolations. Third law values calculated using statistical mechanical thermodynamic functions are in much better agreement with values obtained from ionization energies and ion energetics. These experiments demonstrate that laser ablation production with direct VUV ionization measurements is a versatile tool to measure ionization energies and bond dissociation energies for catalytically interesting species such as metal oxides and carbides.     

Combined vacuum ultraviolet laser and synchrotron pulsed field ionization study of CH2BrCl

The pulsed field ionization-photoelectron (PFI-PE) spectrum of bromochloromethane (CH2BrCl) in the region of 85,320-88,200 cm-1 has been measured using vacuum ultraviolet laser. The vibrational structure resolved in the PFI-PE spectrum was assigned based on ab initio quantum chemical calculations and Franck-Condon factor predictions. At energies 0-1400 cm-1 above the adiabatic ionization energy (IE) of CH2BrCl, the Br-C-Cl bending vibration progression (nu1+=0-8) of CH2BrCl+ is well resolved and constitutes the major structure in the PFI-PE spectrum, whereas the spectrum at energies 1400-2600 cm-1 above the IE(CH2BrCl) is found to exhibit complex vibrational features, suggesting perturbation by the low lying excited CH2BrCl+(A 2A") state. The assignment of the PFI-PE vibrational bands gives the IE(CH2BrCl)=85,612.4+/-2.0 cm-1 (10.6146+/-0.0003 eV) and the bending frequencies nu1+(a1')=209.7+/-2.0 cm-1 for CH2BrCl+(X2A'). We have also examined the dissociative photoionization process, CH2BrCl+hnu-->CH2Cl++Br+e-, in the energy range of 11.36-11.57 eV using the synchrotron based PFI-PE-photoion coincidence method, yielding the 0 K threshold or appearance energy AE(CH2Cl+)=11.509+/-0.002 eV. Combining the 0 K AE(CH2Cl+) and IE(CH2BrCl) values obtained in this study, together with the known IE(CH2Cl), we have determined the 0 K bond dissociation energies (D0) for CH2Cl+-Br (0.894+/-0.002 eV) and CH2Cl-Br (2.76+/-0.01 eV). We have also performed CCSD(T, full)/complete basis set (CBS) calculations with high-level corrections for the predictions of the IE(CH2BrCl), AE(CH2Cl+), IE(CH2Cl), D0(CH2Cl+-Br), and D0(CH2Cl-Br). The comparison between the theoretical predictions and experimental determinations indicates that the CCSD(T, full)/CBS calculations with high-level corrections are highly reliable with estimated error limits of <17 meV.     

A mass spectrometric and density functional study of the intermetallic molecules AuBe, AuMg, and AuCa

The intermetallic molecules AuBe and AuCa were identified by means of the Knudsen-Effusion Mass Spectrometry technique in the high-temperature vapors produced by vaporizing Au-Be-Ca alloys of proper composition. The gaseous equilibria AuBe(g)+Au(g)=Au(2)(g)+Be(g) and AuCa(g)+Au(g)=Au(2)(g)+Ca(g) were studied in the temperature ranges 1720-1841 K and 1669-1841 K, respectively, by monitoring the partial pressures of all the species involved. The equilibrium data were analyzed by the third-law method, obtaining for the first time the dissociation energy D(0) ( composite function) of the two intermetallic species: D(0) ( composite function)(AuBe)=234.0+/-4.0 kJ/mol; D(0) ( composite function)(AuCa)=246.7+/-4.0 kJ/mol. These values are significantly higher than the recently published D(0) ( composite function) of the species AuMg (175.4+/-2.7 kJ/mol). Furthermore, the ionization energies (IE) of AuBe, AuMg, and AuCa were obtained by measuring the electron impact ionization efficiency curves, IE(AuBe)=7.5+/-0.3 eV, IE(AuMg)=6.7+/-0.3 eV, and IE(AuCa)=5.5+/-0.3 eV. Theoretical calculations were also carried out for these species by density functional theory methods (PW91 and BP86) used in conjunction with Stuttgart relativistic effective core potentials. Both functionals were found to perform very well in reproducing experimental D(0) ( composite function), IE, and molecular parameters.     

Ab initio study of low-lying electronic states of SnCl2+

Complete active space self-consistent field (CASSCF), multireference configuration interaction (MRCI), and restricted-spin coupled-cluster singles-doubles with perturbative triples [RCCSD(T)] calculations have been carried out on low-lying doublet and quartet states of SnCl2+, employing basis sets of up to aug-cc-pV5Z quality. Effects of core correlation and off-diagonal spin-orbit interaction on computed vertical ionization energies were investigated. The best theoretical estimate of the adiabatic ionization energy (including zero-point vibrational energy correction) to the X2A1 state of SnCl2+ is 10.093+/-0.010 eV. The first photoelectron band of SnCl2 has also been simulated by employing RCCSD(T)/aug-cc-pV5Z potential energy functions and including Duschinsky rotation and anharmonicity.     

Threshold-photoelectron spectroscopic study of methyl-substituted hydrazine compounds

The valence shell electronic structures of methylhydrazine (CH(3)NHNH(2)), 1,1-dimethylhydrazine ((CH(3))(2)NNH(2)) and tetramethylhydrazine ((CH(3))(4)N(2)) have been studied by recording threshold and conventional (kinetic energy resolved) photoelectron spectra. Ab initio calculations have been performed on ammonia and the three methyl substituted hydrazines, with the structures being optimized at the B3-LYP/6-31+G(d) level of theory. The ionization energies of the valence molecular orbitals were calculated using the Green's function method, allowing the photoelectron bands to be assigned to specific molecular orbitals. The ground-state adiabatic and vertical ionization energies, as determined from the threshold photoelectron spectra, were IE(a) = 8.02 +/- 0.16 eV and IE(v) = 9.36 +/- 0.02 eV for methylhydrazine, IE(a) = 7.78 +/- 0.16 eV and IE(v) = 8.86 +/- 0.01 eV for 1,1-dimethylhydrazine and IE(a) = 7.26 +/- 0.16 eV and IE(v) = 8.38 +/- 0.01 eV for tetramethylhydrazine. Due to the large geometry change that occurs upon ionization, these IE(a) values are all higher than the true thresholds. New features have been observed in the inner valence region and these have been compared with similar structure in the spectrum of hydrazine. The effect of resonant autoionization on the threshold photoelectron yield is discussed. New heats of formation (Delta(f)H) are proposed for the three hydrazines on the basis of G3 calculations: 107, 94, and 95 kJ/mol for methylhydrazine, 1,1-dimethyhydrazine and tetramethylhydrazine, respectively. The previously reported Delta(f)H for tetramethylhydrazine is shown to be erroneous.     

On the formation of radical dications of protonated amino acids in a "microsolution" of water or acetonitrile and their reactivity towards the solvent

In high-energy collisions (50 keV) between O2 and protonated amino acids AH+, radical dications AH2+* are formed for A = Phe, His, Met, Tyr, and Trp. When solvated by water or acetonitrile (S), AH2+*(S)1,2 are formed for A = Arg, His, Met, Tyr, and Trp. The stability of the hydrogen-deficient AH2+* in the "microsolution" depends on the energetics of the electron transfer reaction AH2+* +S --> AH++S+*, the hydrogen abstraction reaction AH2+*+S --> AH2(2+)+[S-H]*, and the proton transfer reaction AH2+* + S --> A+*+SH+. Using B3LYP/ 6-311+G(2d,p)//B3LYP/6-31+G(d) model chemistry, we describe these three reactions in detail for A=Tyr and find that the first two reactions are unfavorable whereas the third one is favorable. However, energy is required for the formation of Tyr+* and SH+ from TyrH2+*(S) to overcome the Coulomb barrier, which renders the complex observable with a life-time larger than 5 micros. The ionization energy, IE, of TyrH+ is calculated to be 11.1 eV in agreement with an experimental measurement of 10.1+/-2.1 eV ([IE(CH3CN)+IE(Tyr)]/ 2); hydration further lowers the IE by 0.3 eV [IE(TyrH+(H2O) = 10.8 eV, calculated]. We estimate the ionization energies of TrpH+, HisH+, and MetH+ to be 10.1+/-2.1 eV, 12.4+/-0.2 eV, and 12.4+/-0.2 eV, and that of PheH+ to be larger than 12.6 eV.     

Ionization energies of multiply protonated polypeptides obtained by tandem ionization in Fourier transform mass spectrometers

Ionization energies (IE) of [M + zH](z+) (z+) electrospray-produced polypeptides were determined by electron ionization in a Penning cell of 4.7 and 9.4 T Fourier transform mass spectrometers. For z = 1+ and substance P, the found IE value of 11.0 +/- 0.4 eV is in agreement with that obtained earlier for ions generated with matrix-assisted laser desorption/ionization. For higher z, the following values were found: 11.7 +/- 0.3 eV for 2+ of [Arg-8]-vasopressin, 11.1 +/- 0.6 eV for 2+ of substance P, 12.2 +/- 0.7 eV for 2+ of renin substrate, 13.3 +/- 0.4 eV for 3+ of B-chain of insulin and 14.6 +/- 0.6 eV for 4+ and 15.1 +/- 0.4 eV for 5+ of melittin. It was found that 90% of existing IE data on polypeptides in the 1.0-3.5 kDa mass range are described with 相似文献   

Theoretical prediction of the ionization energies of the C4H7 radicals: 1-methylallyl, 2-methylallyl, cyclopropylmethyl, and cyclobutyl radicals

The ionization energies (IEs) for the 1-methylallyl, 2-methylallyl, cyclopropylmethyl, and cyclobutyl radicals have been calculated by the wave function based ab initio CCSD(T)/CBS approach, which involves the approximation to the complete basis set (CBS) limit at the coupled cluster level with single and double excitations plus quasiperturbative triple excitation [CCSD(T)]. The zero-point vibrational energy correction, the core-valence electronic correction, and the scalar relativistic effect correction are included in these calculations. The present CCSD(T)/CBS results are then compared with the IEs determined in the photoelectron experiment by Schultz et al. [J. Am. Chem. Soc. 106, 7336 (1984)] The predicted IE value (7.881 eV) of 2-methylallyl radical is found to compare very favorably with the experimental value of 7.90+/-0.02 eV. Two ionization transitions for cis-1-methylallyl and trans-1-methylallyl radicals have been considered here. The comparison between the predicted IE values and the previous measurements shows that the photoelectron peak observed by Schultz et al. likely corresponds to the adiabatic ionization transition for the trans-1-methylallyl radical to form trans-1-methylallyl cation. Although a precise IE value for the cyclopropylmethyl radical has not been directly determined, the experimental value deduced indirectly using other known energetic data is found to be in good accord with the present CCSD(T)/CBS prediction. We expect that the Franck-Condon factor for ionization transition of c-C4H7-->bicyclobutonium is much less favorable than that for ionization transition of c-C4H7-->planar-C4H7+, and the observed IE in the previous photoelectron experiment is likely due to the ionization transition for c-C4H7-->planar-C4H7+. Based on our CCSD(T)/CBS prediction, the ionization transition of c-C4H7-->bicyclobutonium with an IE value around 6.92 eV should be taken as the adiabatic ionization transition for the cyclobutyl radical. The present study provides support for the conclusion that the CCSD(T)/CBS approach with high-level energetic corrections can be used to provide reliable IE predictions for C4 hydrocarbon radicals with an uncertainty of +/-22 meV. The CCSD(T)/CBS predictions to the heats of formation for the aforementioned radicals and cations are also presented.     

Spectroscopic constants and potential energy curves of yttrium carbide (YC)

The potential energy curves of the low-lying electronic states of yttrium carbide (YC) and its cation are calculated at the complete active space self-consistent field and the multireference single and double excitation configuration interaction (MRSDCI) levels of theory. Fifteen low-lying electronic states of YC with different spin and spatial symmetries were identified. The X (4)Sigma- state prevails as the ground state of YC, and a low-lying excited A (4)Pi state is found to be 1661 cm(-1) higher at the MRSDCI level. The computations of the authors support the assignment of the observed spectra to a B (4)Delta(Omega=72)<--A (4)Pi(Omega=52) transition with a reinterpretation that the A (4)Pi state is appreciably populated under the experimental conditions as it is less than 2000 cm(-1) of the X (4)Sigma- ground state, and the previously suggested (4)Pi ground state is reassigned to the first low-lying excited state of YC. The potential energy curves of YC+ confirm a previous prediction by Seivers et al. [J. Chem. Phys. 105, 6322 (1996)] that the ground state of YC+ is formed through a second pathway at higher energies. The calculated ionization energy of YC is 6.00 eV, while the adiabatic electron affinity is 0.95 eV at the MRSDCI level. The computed ionization energy of YC and dissociation energy of YC+ confirm the revised experimental estimates provided by Seivers et al. although direct experimental measurements yielded results with greater errors due to uncertainty in collisional cross sections for YC+ formation.     

Revision of the second ionization energy of toluene

Charge stripping (CS) of the molecular ion of toluene, C(7)H(8) (+)-->C(7)H(8) (2+)+e, is often used as a reference for the determination of second ionization energies in energy-resolved CS experiments. For calibration of the kinetic energy scale, a value of IE(C(7)H(8) (+))=(15.7+/-0.2) eV derived from the appearance energy of the toluene dication upon electron ionization has been accepted generally. Triggered by some recent discrepancies between CS measurements on the one hand and different experimental methods as well as theoretical predictions on the other, we have reinvestigated the photon-induced double ionization of toluene using synchrotron radiation. These photoionization measurements yield phenomenological appearance energies of AE(C(7)H(8) (+))=(8.81+/-0.03) eV for the monocation and AE(C(7)H(8) (2+))=(23.81+/-0.06) eV for the dication. The former is in good agreement with a much more precise spectroscopic value, IE(C(7)H(8))=(8.8276+/-0.0006) eV. Explicit consideration of the Franck-Condon envelopes associated with photoionization to the dication in conjunction with the application of the Wannier law leads to an adiabatic ionization energy IE(a)(C(7)H(8) (+))=(14.8+/-0.1) eV, which is as much as 0.9 eV lower than the previous value derived from electron ionization. Because in many previous CS measurements the transition C(7)H(8) (+)-->C(7)H(8) (2+)+e was used as a reference, the energetics of several gaseous dications might need some readjustment.     

Ionization energies of hypervalent Li2F,Li2Cl and Na2Cl molecules obtained by surface ionization electron impact neutralization mass spectrometry

Ionization energies of hypervalent Li(2)F, Li(2)Cl and Na(2)Cl molecules detected by surface ionization electron impact neutralization mass spectrometry are reported. The ionization energies were 3.78 +/- 0.2 eV for Li(2)F, 4.93 +/- 0.2 eV for Li(2)Cl, and 4.21 +/- 0.2 eV for Na(2)Cl. The ionization energies (IE) agree with theoretical ionization energies calculated by ab initio methods, supporting the theoretical prediction that Li(2)F has a hyperlithiated configuration in which the odd electron delocalizes over the two lithiums and with photoionization measurement. The first ionization energy of Na(2)Cl was experimentally confirmed earlier and for Li(2)Cl as well.8 We have developed and used this new approach for the problem--in the present work ions were first formed by surface ionization, followed by electron attachment (neutralization).     

Ion chemistry of OV(OCH3)3 in the gas phase: molecular cations and anions and their primary fragmentations

Trimethyl vanadate(V), OV(OCH(3))(3) (1), is examined by various mass spectrometric means. Photoionization experiments yield an ionization energy of IE(OV(OCH(3))(3)) = 9.54 +/- 0.05 eV for the neutral molecule. The primary fragmentation of the molecular cation 1(+), i.e., loss of neutral formaldehyde, can occur via two independent routes of hydrogen migrations to afford the formal V(IV) compounds HOV(OCH(3))(2)(+) and OV(OCH(3))(CH(3)OH)(+), respectively. These two pathways are associated with low-lying activation barriers of almost identical height. At elevated energies, direct V-O bond cleavage of 1(+) allows for expulsion of a methoxy radical concomitant with the generation of the cationic fragment OV(OCH(3))(2)(+), a formal V(V) compound. Trimethyl vanadate can also form a molecular anion, 1(-), whose most abundant dissociation channel involves loss of a methyl radical, thereby leading to the formal V(V) compound OV(OCH(3))(2)O(-). Various mass spectrometric experiments and extensive theoretical studies provide detailed insight into the ion structures and the relative energetics of the primary dissociation reactions of the molecular cations and anions of 1.     

Description of the geometric and electronic structures responsible for the photoelectron spectrum of FeO4(-)

The relative stabilities of all low-lying conformations of FeO(4)(0/-) stoichiometry were investigated at the quantum mechanical BPW91, CASPT2, and RCCSD(T) levels of theory. For both the anionic and neutral clusters, the determination of the most stable structure appears to be a demanding task. The density functional theory and wave function second-order perturbation theory computational techniques place the doublet state of the tetrahedron-like O(4)Fe(-) conformation substantially lower, up to 0.81 eV, than the doublet state of η(2)-(O(2))FeO(2)(-). The coupled-cluster method reduces the energy difference to less than 0.01 eV. This equal stability of the ground states of O(4)Fe(-) and η(2)-(O(2))FeO(2)(-) leads to the assignment of the experimental photoelectron spectrum of FeO(4)(-). The lowest binding energy band (X band) is ascribed to the (2)A(1) → (1)A(1) ionization of η(2)-(O(2))FeO(2)(-), while the higher energy band (A band) mainly corresponds to the (2)E → (1)A(1) transition between the O(4)Fe(0/-) conformations. For a specific conformation, CASPT2 calculates the best electron detachment energies. The highest energy peak in this band with the weakest intensity could be ascribed to the (2)A(2) → (3)A(2) transition between the η(2)-(O(2))FeO(2) conformations. The two progressions are the result of ionizations from the anti-bonding orbitals of predominant iron 3d. For a specific conformation, CASPT2 calculates the best electron detachment energies. A BPW91 Franck-Condon simulation of the observed vibrational progressions further confirms the proposed assignments.     

Single and double photoionizations of methanal (formaldehyde)

Single and double photoionization spectra of formaldehyde have been measured at 40.81 and 48.37 eV photon energy and the spectrum of the doubly charged cation has been interpreted using high-level electronic structure calculations. The adiabatic double-ionization energy is determined as 31.7+/-0.25 eV and the vertical ionization energy is 33 eV. The five lowest excited electronic states are identified and located. The potential-energy surfaces of the accessible states explain the lack of stable H2CO2+ dications and the lack of vibrational structure. The experimental double-ionization spectrum can be decomposed into two distinct contributions, one from direct photoionization and the second from indirect double photoionization by an inner-valence shell Auger effect.     

ZEKE-PFI spectroscopy of benzocaine

The adiabatic ionization threshold (AIT) of trans- and gauche-benzocaine has been measured by zero electron kinetic energy-pulsed field ionization (ZEKE-PFI) spectroscopy to be 7.8412+/-0.0008 eV (lasers at 34,134.4 and 29,109.3 cm(-1)) and 7.8421+/-0.0004 eV (34,144.8+29105.7 cm(-1)), respectively. AITs computed at the B3LYP/AUG-cc-p-VDZ level for the two conformers are some approximately 2,500 cm(-1) lower than the experimental; in contrast their energy difference is very close. The trans-benzocaine cation ZEKE spectra has been recorded taking a number of S(1) intermediate vibronic states. The spectra provide an energy threshold for the appearance of intramolecular vibrational redistribution (IVR) around approximately 540 cm(-1) in the S(1) state.     

Theoretical studies of the electronic spectrum of SiC

Ab initio based multireference singles and doubles configuration interaction calculations have been carried out to study the electronic structure and spectroscopic properties of the SiC⁺ ion. Potential energy curves and spectroscopic constants (r_e, T_e, ω_e) of 14 low-lying doublet and quartet states of the ion are studied. The spin-orbit coupling has been included to see its effects on the spectroscopic properties. Transition probabilities of some quartet–quartet transitions are computed, while the spin-forbidden transitions are very weak. Dipole moments of all low-lying states are estimated by keeping the origin at the center of mass. The vertical and adiabatic ionization energies of SiC are also reported.     

Cation spectroscopy and binding energy determination for 1,4-benzodioxan-Ar1 and -Ar2 complexes

Cation vibronic spectra are measured for 1,4-benzodioxan (BZD) and van der Waals complexes of BZD with one and two Ar atoms using zero electron kinetic energy and mass analyzed threshold ionization spectroscopy. The spectra of the monomer cation were used to measure the frequencies of the two key low-frequency modes which had previously been extensively studied in the neutral S0 and S1 states. The aliphatic ring twisting mode, nu25, has an energy of 146 cm(-1) in the cation, intermediate between the values found in the S0 and S1 states. The bending, butterfly-like mode nu48 has an energy of 125 cm(-1), which is of higher frequency than either of the neutral states. The S1 spectra of the BZD-Ar1 and BZD-Ar2 complexes are recorded and observed to have modest red shifts from the monomer. The cation spectra of the complexes are also measured using mass analyzed threshold ionization spectroscopy including scans at higher energy which are used to determine the Ar binding energies. The energies for the loss of one Ar atom were determined to be 630 +/- 10 and 650 +/- 10 cm(-1) for BZD-Ar and BZD-Ar2, respectively. The similar cation spectra and similar binding energies indicate that each Ar atom in BZD-Ar2 has a similar binding geometry. Quantum chemical calculations were performed which had fair agreement with the measured binding energies and give some insight into the specific binding geometry.     

VUV photoelectron imaging of biological nanoparticles: ionization energy determination of nanophase glycine and phenylalanine-glycine-glycine

The ionization energies of biological nanoparticles are determined using the velocity map photoelectron imaging technique. A beam of nanoparticles produced by aerosol methods is photoionized with tunable vacuum ultraviolet (VUV) synchrotron radiation. The resulting photoelectrons are detected and their angular and energy distributions are measured, yielding an angle-resolved photoelectron spectrum. The ionization energies of the nanoparticles are derived from plots of the photoelectron spectrum versus incident photon energy. The ionization energies of nanophase glycine and phenylalanine-glycine-glycine are 7.6 +/- 0.2 eV, and 7.5 +/- 0.2 eV, respectively. X-Ray powder diffraction studies on the glycine nanoparticles indicate that they are crystalline in nature. The reduced ionization energy when compared to gas phase results suggests that the polarization energy in the solid is significant. The difference in the ionization energy between the nano and gas phase reflects this polarization energy and is derived to be 1.7 +/- 0.2 eV and 1.6 +/- 0.2 eV for glycine and phenylalanine-glycine-glycine, respectively. Using these results the molecular polarizability of glycine is estimated to be 4.7 +/- 0.3 A3 (31.9 +/- 1.9 au).     

Probing the electronic structure of UO+ with high-resolution photoelectron spectroscopy

The pulsed field ionization-zero kinetic energy photoelectron technique has been used to observe the low-lying energy levels of UO+. Rotationally resolved spectra were recorded for the ground state and the first nine electronically excited states. Extensive vibrational progressions were characterized. Omega+ assignments were unambiguously determined from the first rotational lines identified in each vibronic band. Term energies, vibrational frequencies, and anharmonicity constants for low-lying energy levels of UO+ are reported. In addition, accurate values for the ionization energies for UO [48,643.8(2) cm(-1)] and U [49,957.6(2) cm(-1)] were determined. The pattern of low-lying electronic states for UO+ indicates that they originate from the U3+(5f3)O2- configuration, where the uranium ion-centered interactions between the 5f electrons are significantly stronger than interactions with the intramolecular electric field. The latter lifts the degeneracy of U3+ ion-core states, but the atomic angular momentum quantum numbers remain reasonably well defined.     

Electronic states of SnS and SnS+: a configuration interaction study

Ab initio based multireference configuration interaction calculations are carried out for SnS and its monopositive ion using effective core potentials. Potential energy curves and spectroscopic constants of the low-lying states of SnS and SnS+ are computed. The ground-state dissociation energies of the neutral and ionic species are about 4.71 and 2.86 eV, respectively which compare well with the available thermochemical data. The effect of d-electron correlation on the spectroscopic constants of a few low-lying states has been studied. The spin-orbit interaction has also been included to investigate its effect on the spectroscopic properties of both SnS and SnS+. Dipole moment and transition moment curves are also constructed as a function of the bond length. Transition probabilities of some dipole-allowed and spin-forbidden transitions are studied. Radiative lifetimes of a few low-lying states are estimated. The E1sigma+-X1sigma+ transition of SnS is predicted to be the strongest one. The components of the A2sigma(+)(1/2)-X2(2)pi(1/2) transition with parallel and perpendicular polarization are separately analyzed. The vertical ionization energies of the ground-state SnS to the ground and low-lying excited states of the monopositive ion are calculated.