Electronic spectroscopy of the 3d Rydberg states of NO-Rg (Rg=Ne,Ar,Kr,Xe) van der Waals complexes

We have employed (2+1) resonance-enhanced multiphoton ionization spectroscopy to record electronic absorption spectra of NO-Rg (Rg=Ne,Ar,Kr) van der Waals complexes. The nitric oxide molecule is the chromophore, and the excitation corresponds to an electron being promoted from the 2ppi* orbital to 3dsigma, 3dpi, and 3ddelta Rydberg states. We review the ordering of the 3dlambda states of NO and use this as a basis for discussing the 3d components in the NO-Rg complexes, in terms of the interactions between the Rydberg electron, the core, and the Rg atom. Predissociation of the H' 2Pi state occurs through the F2Delta state for NO-Ar and NO-Kr, and this will be considered. We shall also outline problems encountered when trying to record similar spectra for NO-Xe, related to the presence of atomic Xe resonances.     

Electronic spectroscopy of NO-(Rg)x complexes (Rg = Ne,Ar) via the 4s and 3d Rydberg states

We have employed (2 + 1) resonance enhanced multiphoton ionization spectroscopy to investigate the 3d and 4s Rydberg states of the NO molecule when bound to the surface of Rg(x) clusters (Rg = rare gas). We observe that the spectra of the NO-Ar(x) species converge in appearance as x increases, and this is discussed in terms of two Rg atoms interacting with the NO+ core, with other Rg atoms being "outside" the Rydberg orbital. We show that the interaction of each of the Rg atoms with the NO is essentially independent for the NO-Rg2 complexes: both by comparing our spectra for Rydberg states of NO-Rg and NO-Rg2, and from the results of ab initio calculations on NO+ - Rg and NO+ - Rg2. In addition, we discuss the disappearance of some electronic bands upon complexation in terms of Franck-Condon factors that are very sensitive to the angular coordinate. We relate our results to those of the bulk by comparing to the previously reported electronic spectroscopy of NO in both Rg matrices and He nanodroplets.     

Ab initio ground- and excited-state intermolecular potential energy surfaces for the NO-Ne and NO-Ar van der Waals complexes

The ground- [NO(X(2)Π)] and excited-state [NO(A(2)Σ(+))] intermolecular potential energy surfaces (IPESs) of the NO-Ne and NO-Ar van der Waals complexes are evaluated using the RCCSD(T) spin-restricted coupled cluster method and d-aug-cc-pVQZ basis set extended with a set of 3s3p2d1f1g midbond functions. These bases are selected from the results of a systematic basis-set convergence study carried out for the NO(A(2)Σ(+))-Ar state. We fit the interaction energies to analytic functions and compare the results to those previously available. The NO-Ar (NO-Ne) IPESs are characterized by absolute minima of -120 and -75 cm(-1) (-58 and -5 cm(-1)) at the ground and first excited state, respectively, located close to the T-shaped geometries for the ground states and at linear dispositions in the case of the excited states. The potentials are further used in the evaluation of the rovibrational spectra of the complexes, and the results are compared to those available in the literature.     

Optical-optical double resonance photoionization spectroscopy of nf Rydberg states of nitric oxide

The spectra of vibrationally excited nf Rydberg states of nitric oxide were recorded by monitoring the photoion current produced using two-photon double resonance excitation via the NO A (2)Sigma(+) state followed by photoexcitation of the Rydberg state that undergoes autoionization. The optical transition intensities from NO A state to nf Rydberg states were calculated, and the results agree closely with experiment. These results combined with circular dichroism measurements allow us to assign rotational quantum numbers to the nf Rydberg states even in a spectrum of relatively low resolution. We report the positions of these nf (upsilon,N,N(c)) Rydberg levels converging to the NO X (1)Sigma(+) upsilon(+) = 1 and 2 ionization limits where N is the total angular momentum excluding electron and nuclear spin and N(c) represents the rotational quantum number of the ion core. Our two-color optical-optical double resonance measurements cover the range of N from 15 to 28, N(c) from 14 to 29, and the principal quantum number n from 9 to 21. The electrostatic interaction between the Rydberg electron and the ion core is used to account for the rotational fine structure and a corresponding model is used to fit the energy levels to obtain the quadrupole moment and polarizability of the NO(+) core. Comparison with a multichannel quantum defect theory fit to the same data confirms that the model we use for the electrostatic interaction between the nf Rydberg electron and the ion core of NO well describes the rotational fine structure.     

Laser spectroscopic studies of several Rydberg states of MgO

We report extensive spectroscopic measurements of rovibronic transitions from the MgO X 1Sigma+ ground state to the high-energy E 1Sigma+, F 1Pi1, and G 1Pi1 Rydberg states. Perturbations in the E 1Sigma+ and G 1Pi1 states were observed. The Rydberg molecular orbital character of the three states is examined, given ab initio calculations by Thummel et al. [Chem. Phys. 129, 417 (1989)]. It is concluded that the E 1Sigma+ and G 1Pi1 states consist primarily of the MgO+ X 2Pi ionic core, surrounded by 3ppi and 3psigma Rydberg electron clouds, respectively, and that the F 1Pi1 state consists primarily of the MgO+ A 2Sigma+ ionic core surrounded by a 3ppi Rydberg electron cloud. Spectroscopic characterizations of some unassigned vibrational levels of analogous MgO 3Pi2 states in this energy region are also reported.     

The binding energies of NO-Rg (Rg = He, Ne, Ar) determined by velocity map imaging

We report velocity map imaging measurements of the binding energies, D(0), of NO-Rg (Rg = He, Ne, Ar) complexes. The X state binding energies determined are 3.0 ± 1.8, 28.6 ± 1.7, and 93.5 ± 0.9 cm(-1) for NO-He, -Ne, and -Ar, respectively. These values compare reasonably well with ab initio calculations. Because the ?-X transitions were unable to be observed for NO-He and NO-Ne, values for the binding energies in the ? state of these complexes have not been determined. Based on our X state value and the reported ?-X origin band position, the ? state binding energy for NO-Ar was determined to be 50.6 ± 0.9 cm(-1).     

Superexcited state reconstruction of HCl using photoelectron and photoion imaging

The velocity-map imaging technique was used to record photoelectron and photofragment ion images of HCl following two-photon excitation of the E Sigma(+)(0+), V 1Sigma(+)(0+) (nu=9,10,11) states and subsequent ionization. The images allowed us to determine the branching ratios between autoionization and dissociation channels for the different intermediate states. These branching ratios can be explained on the basis of intermediate state electron configurations, since the configuration largely prohibits direct ionization in a one-electron process, and competition between autoionization and dissociation into H* (n=2)+Cl and H+Cl*(4s,4p,3d) is observed. From a fit to the vibrationally resolved photoelectron spectrum of HCl+ it is apparent that a single superexcited state acts as a gateway to autoionization and dissociation into H+Cl*(4s). Potential reconstruction of the superexcited state to autoionization was undertaken and from a comparison of different autoionization models it appears most likely that the gateway state is a purely repulsive and low-n Rydberg state with a (4Pi) ion core.     

Full configuration interaction calculation of the low lying valence and Rydberg states of BeH

The all-electron full configuration interaction (FCI) vertical excitation energies for some low lying valence and Rydberg excited states of BeH are presented in this article. A basis set of valence atomic natural orbitals has been augmented with a series of Rydberg orbitals that have been generated as centered onto the Be atom. The resulting basis set can be described as 4s2p1d/2s1p (Be/H) + 4s4p3d. It allows to calculate Rydberg states up to n= {3,4,5} of the s, p, and d series of Rydberg states. The FCI vertical ionization potential for the same basis set and geometry amounts to 8.298 eV. Other properties such as FCI electric dipole and quadrupole moments and FCI transition dipole and quadrupole moments have also been calculated. The results provide a set of benchmark values for energies, wave functions, properties, and transition properties for the five electron BeH molecule. Most of the states have large multiconfigurational character in spite of their essentially single excited nature and a number of them present an important Rydberg-valence mixing that is achieved through the mixed nature of the particle MO of the single excitations.     

The Ã-state dissociation continuum of NO-Ar and its near infrared spectrum

After preparing NO-Ar in a vibrational state correlating with the first overtone vibration in NO, we recorded its hot band UV spectrum by monitoring simultaneously the intensity in the NO(+) and the NO(+)-Ar ion channels. In this way, the bound as well as the continuous part of the electronic A?←X? spectrum are observed directly. Below the dissociation threshold, the intensity is found exclusively in the NO(+)-Ar ion channel while above it is found in the NO fragment ion channel. We observe simultaneously intensity in both ion channels only for a very narrow frequency range near the dissociation threshold. Structures in the dissociation spectrum correlate well with the thresholds for production of NO(A) in different rotational states. At frequencies well above the dissociation threshold, NO-Ar is detected efficiently as a NO fragment. This fact has been exploited to record the near IR spectrum of NO-Ar with significantly increased sensitivity. The dissociation detected spectra are essentially identical to our previous constant photon energy sum (CONPHOENERS) scans [B. Wen, Y. Kim, H. Meyer, J. K?os, and M. H. Alexander, J. Phys. Chem. A 112, 9483 (2008)]. Several hot band spectra have been remeasured with improved sensitivity enabling a comprehensive analysis yielding for the first time spectroscopic constants for levels associated with the potential surfaces of NO-Ar correlating with NO(v(NO) = 0 and 2). Since many NO-X complexes do not have a strong bound A?-state spectrum, although they do have a A?-state dissociation continuum, there is the possibility to record their near IR spectra by employing dissociation detection.     

Orbital relaxation in the Rydberg series of the lithium atom. An excited state SCF calculation

Self-consistent-field (SCF ) calculations for a series of Rydberg states (1s²ns)²S of the Li atom are performed using the generalized Brillouin theorem (GBT) method. The calculated energy is a proper upper bound to the excited state energy. The SCF term values of the Rydberg states are almost the same as those of the frozen-core approximation ones. The orbital behavior shows that the core is slightly expanded by the penetration of the Rydberg orbitals, and the higher Rydberg orbitals can be very well represented by the modified hydrogen-like orbitals.     

Coherent polyatomic dynamics studied by femtosecond time-resolved photoelectron spectroscopy: dissociation of vibrationally excited CS2 in the 6s and 4d Rydberg states

The dissociation dynamics of the 6s and 4d Rydberg states of carbon disulfide (CS(2)*) are studied by time-resolved photoelectron spectroscopy. The CS(2) is excited by two photons of 267 nm (pump) to the 6s and 4d Rydberg states and probed by ionization with either 800 or 400 nm. The experiments can distinguish and successfully track the time dynamics of both spin [1/2] (upper) and [3/2] (lower) cores of the excited Rydberg states, which are split by 60 meV, by measuring the outgoing electron kinetic energies. Multiple mode vibrational wave packets are created within the Rydberg states and observed through recurrence interferences in the final ion state. Fourier transformation of the temporal response directly reveals the coherent population of several electronic states and vibrational modes. The composition of the wave packet is varied experimentally by tuning the excitation frequency to particular resonances between 264 and 270 nm. The work presented here shows that the decay time of the spin components exhibits sensitivity to the electronic and vibrational states accessed in the pump step. Population of the bending mode results in an excited state lifetime of as little as 530 fs, as compared to a several picosecond lifetime observed for the electronic origin bands. Experiments that probe the neutral state dynamics with 400 nm reveal a possible vibrationally mediated evolution of the wave packet to a different Franck-Condon window as a consequence of Renner-Teller splitting. Upon bending, symmetry lowering from D(infinityh) to C(2v) enables ionization to the CS(2) (+) (B (2)Pi(u)) final state. The dissociation dynamics observed are highly mode specific, as revealed by the frequency and temporal domain analysis of the photoelectron spectra.     

Rydberg electron transfer to C6H5NO2: lifetimes and characteristics of the product C6H5NO2- ions

The nature of electron binding in C6H5NO2- ions produced by Rydberg electron transfer in K(np)C6H5NO2 collisions is investigated through measurements of the number and the lifetimes of the product ions and their dependence on Rydberg atom velocity and principal quantum number n in the range 12 相似文献   

Vacuum ultraviolet excitation spectroscopy of the autoionizing Rydberg states of atomic sulfur in the 73 350-84 950 cm(-1) frequency range

The photoionization efficiency (PIE) spectra of metastable sulfur (S) atoms in the 1 D and 1 S states have been recorded in the 73 350-84 950 cm(-1) frequency range by using a velocity-mapped ion imaging apparatus that uses a tunable vacuum ultraviolet laser as the ionization source. The S(1 D) and S(1 S) atoms are produced by the 193 nm photodissociation of CS2. The observed PIE spectra of S(1 D) and S(1 S) shows 35 autoionizing resonances with little or no contribution from direct photoionization into the S+(4S 3/2)+e(-) ionization continuum. Velocity-mapped ion images of the S+ at the individual autoionizing Rydberg resonances are used to distinguish whether the lower state of the resonance originates from the 1 D, 1 S, or 3P states. The analysis and assignment of the Rydberg peaks revealed 22 new Rydberg states that were not previously known. The autoionization lifetimes tau of the Rydberg states are derived from the linewidths by fitting the lines with the Fano formula. Deviations from the scaling law of tau(n*) proportional to, n*3, where n* is the effective quantum number of the Rydberg state, are observed. This observation is ascribed to perturbations by nearby triplet Rydberg states, which shorten the autoionization lifetimes of the singlet Rydberg levels.     

Rydberg atom mediated polar molecule interactions: a tool for molecular-state conditional quantum gates and individual addressability

We study the possibility to use interaction between a polar molecule in the ground electronic and vibrational state and a Rydberg atom to construct two-qubit gates between molecular qubits and to coherently control molecular states. A polar molecule within the electron orbit in a Rydberg atom can either shift the Rydberg state, or form a Rydberg molecule. Both the atomic shift and the Rydberg molecule states depend on the initial internal state of the polar molecule, resulting in molecular state dependent van der Waals or dipole-dipole interaction between Rydberg atoms. Rydberg atoms mediated interaction between polar molecules can be enhanced up to 10(3) times. We describe how the coupling between a polar molecule and a Rydberg atom can be applied to coherently control molecular states, and specifically, to individually address molecules in an optical lattice, and to non-destructively readout molecular qubits.     

Laser induced amplified spontaneous emission from the B2Pi, L2Pi, and I2Sigma+ valence states of NO

Amplified spontaneous emission (ASE) from single rovibrational levels of valence (non-Rydberg) states of NO molecules has been investigated. The B2Pi (v=24 and 25), L2Pi (v=5 and 6), and I2Sigma+ (v=6) levels have been populated through laser optical-optical double resonance excitation via the Rydberg A2Sigma+ state. Term values for the 2Pi states have been determined with an accuracy of +/-0.03 cm(-1). Analyses of rotationally resolved dispersed ASE spectra in the near infrared region have shown that all the lower states belonged to the Rydberg states. The valence approximately Rydberg coupling in the upper manifolds has driven ASE systems from the valence to the Rydberg levels where they benefit from the strong intensities of inter-Rydberg transitions with Deltav=0. The experimentally predicted valence approximately Rydberg interactions have been compared with theoretical treatments.     

Electronic and cationic states of 2-methylpropene (isobutene) studied by VUV absorption,scattered electron spectroscopy and AB initio multireference configuration interaction calculations

VUV (6.2–9 eV) and electron scattering spectra (1–9 eV) have been recorded for 2-methylpropene (isobutene). Also, electronic states of the molecule, including the ground state and cationic states, have been investigated using ab initio multi-reference configuration interaction calculations. Some Koopmans-type in the UV photoelectron spectrum are reassigned and a number of shake-up states computed. In the electronic spectrum, Rydberg excited have been assigned and a second valence excited state (σ π*) located within about 1 eV of the V(ππ*) state. The experiments show, and theory confirms, that the Rydberg R(π3s) state has a positive electron affinity. Some interesting correlations between ionisation energies, energies of shake-up state electronic excitation energies are identified.     

以(真空紫外光+紫外光)-共振加强式多光子游离法侦测交叉分子束之甲基生成物

用(真空紫外光+紫外光)-共振加强式多光子游离法侦测甲基自由基.为证明此法之灵敏度,实验用交叉分子束反应F+CH4(CD4)→HF(DF)+CH3(CD3),其绝对灵敏度可达107/cm3.由所得之光谱,更精确地得到两个里德堡态3d2E″及3d 2A1′之光谱系数.     

Photofragmentations, state interactions, and energetics of Rydberg and ion-pair states: two-dimensional resonance enhanced multiphoton ionization of HBr via singlet-, triplet-, Ω = 0 and 2 states

Mass spectra were recorded for one-colour resonance enhanced multiphoton ionization (REMPI) of H(i)Br (i = 79, 81) for the two-photon resonance excitation region 79,040-80,300 cm(-1) to obtain two-dimensional REMPI data. The data were analysed in terms of rotational line positions, intensities, and line-widths. Quantitative analysis of the data relevant to near-resonance interactions between the F(1)Δ(2)(v' = 1) and V(1)Σ(+)(v' = m + 7) states gives interaction strengths, fractional state mixing, and parameters relevant to dissociation of the F state. Qualitative analysis further reveals the nature of state interactions between ion-pair states and the E(1)Σ(+) (v' = 1) and H(1)Σ(+)(v' = 0) Rydberg states in terms of relative strengths and J' dependences. Large variety in line-widths, depending on electronic states and J' quantum numbers, is indicative of number of different predissociation channels. The relationship between line-widths, line-shifts, and signal intensities reveals dissociation mechanisms involving ion-pair to Rydberg state interactions prior to direct or indirect predissociations of Rydberg states. Quantum interference effects are found to be important. Moreover, observed bromine atom (2 + 1) REMPI signals support the importance of Rydberg state predissociation channels. A band system, not previously observed in REMPI, was observed and assigned to the k(3)Π(0)(v' = 0) ←← X transition with band origin 80,038 cm(-1) and rotational parameter B(v('))=7.238 cm(-1).