Oпpeдeлehиe othocиteлъhoгo pacпoлoжehия heкomБиhиpyющиx элeкtpohhъix coctoяhий дbyxatomhъix moлeкyл. Ochobhoe элeкtpohhoe coctoяhиe ZrO

A method is proposed for determining the energy difference of noncombining electronic states and the type of ground electronic state of molecules, based on studying the temperature dependence of integral absorption coefficients of molecular bands in a reflected shock wave plasma over a wide range of temperatures. The method is used to determine the relative position of singlet and triplet ZrO electronic states. As the result of measurements of integral absorption coefficients of 0, 0 bands of ${}^1\text{Σ}{}^{\mathrm{+}}\text{-}{}^1\text{Σ}{}^{\mathrm{+}}$ and ${}^3\text{Δ -}{}^3\text{Δ}$ systems in the temperature interval 3370–5200°K, it is shown that ¹Σ⁺ state is the ZrO ground state, whilst T₀(a³Δ) = 1700 ± 250 cm^-1.     

The assignment of molecular infrared spectra from a laser magnetic resonance spectrometer

Mathematical techniques are presented which have proved useful in assigning the laser magnetic resonance pure-rotation spectrum of HO₂, i.e., useful in assigning an absorption spectrum obtained when molecular energy levels are Zeeman shifted by an external magnetic field until transition frequencies coincide with a fixed-frequency radiation source. The techniques described should have general applicability to the laser magnetic resonance vibration-rotation spectrum of any molecule in an orbitally nondegenerate electronic state and a doublet electronic spin state ($\text{S =}\text{1}\text{2}$). Equations involving both Zeeman line positions and Zeeman line intensities are presented. These allow the assignment of M_J quantum numbers, the determination of the spin-rotation interaction constant γ and rotational quantum number N for both the upper and the lower state, and the determination of the zero-field transition frequency. The equations can be used without prior knowledge of the molecular structure or energy levels.     

EPR of photo-excited triplet states: A personal account

A sketch is presented of the path that has led from Zavoisky’s pioneering experiments to modern investigations by electron paramagnetic resonance (EPR) of the phosphorescent (S = 1) triplet state of polyatomic molecules or ions. The group-theoretical method first introduced by Wigner in his analysis of the multiplets of atomic spectroscopy, likewise provides a key for understanding the zero-field splitting and selection rules for radiative decay of the phosphorescent triplet state. Examples to illustrate the progress made through EPR experiments are selected from three fields. (i) Conformational instability on excitation. Both the zero-field splitting and the electron spin density distribution provide unique fingerprints of a triplet state’s geometry — structural information of a kind that is nonexistent for singlet states! Illustrations are provided by benzene C₆H₆ and fullerene C₆₀. (ii) The optical pumping cycle. The spin selectivity of singlet-to-triplet intersystem crossing and radiative decay of the individual spin components of the triplet state is discussed. In practice this selectivity is put to advantage by performing EPR on triplet states in zero-field by means of optical detection. In turn, such experiments have led to a detailed insight into the spin-orbit coupling mechanisms responsible for the spin selectivity of the above processes. The high sensitivity attainable with optical detection has recently culminated in EPR experiments on single molecules. (iii) Quantum interference. In a triplet state of low symmetry two of the spin sublevels may decay to the ground state by the emission of photons of a common polarization (i.e., out of plane for an aromatic hydrocarbon). In such a situation quantum interference between the two decay channels can be induced by an appropriate preparation of the excited state. An example is shown where flash-excitation in the singlet manifold followed by rapid intersystem crossing causes theS = 1 spin angular momentum to be created in a spin state which is not an eigenstate of the zero-field splitting tensor. This nonstationary character of the initial triplet state, which reflects the spin-orbit coupling pathway, is observed through the detection of a spontaneous microwave signal following the 25 ps laser flash.     

A hole-burning study onRhodobacter sphaeroides with absorbance-detected magnetic resonance (ADMR)

The triplet state of the primary donor in mutant reaction centers ofRhodobacter sphaeroides, in which amino acids near the primary donor were substituted, was investigated by absorbance-detected magnetic resonance. (ADMR). The mutations are associated with the substitution of leucines at site L131 and M160 near the bacteriochlorophyll halves of the primary donor by histidines, resulting in the formation of a hydrogen bond with the carbonyl group at ring V of either bacteriochlorophyll halves of the primary donor. For both mutant reaction centers the zero-field splitting parameters were slightly changed compared to native reaction centers, indicating that the dimer-halves of the primary donor in the latter are coupled in the triplet state: In addition, results from hole burning ADMR experiments on the mutants were compared with those forRhodobacter sphaeroides R26. The linewidths of the holes burnt in the zero-field transitions were similar for the mutant reaction centers involving the mutation at site L131 and for reaction centers ofRhodobacter sphaeroides R26; a somewhat larger linewidth was experiments on¹⁴N- and¹⁵N-containing reaction centers ofRhodobacter sphaeroides R26 showed that at high microwave power the holewidths of¹⁴N-reaction centers are determined by the quadrupole lines, but that at low microwave power the holewidths are mainly determined by unresolved hyperfine interactions with the protons. From the similarity in the holewidths for all reaction centers, we therefore conclude that the hyperfine interactions between the protons and the triplet spin, and thus the electronic composition of the triplet state, are similar for all reaction centers studied. The slight differences in the holewidths of the zero-field transitions and in the zero-field splitting parameters of the triplet state of the primary donor, and the differences previously observed for the interaction between the primary donor and neighboring bacteriochlorophylls (Vrieze J., Williams J.C., Allen J.P., Hoff A.J.: Biochim. Biophys. Acta1276, 221–228 (1996)), are attributed to small changes in charge-transfer contributions to the triplet state.     

Isotope effects and novel level crossings observed by ODMR in 6H SiC(Ti)

Optical detection of magnetic resonance (ODMR) and magnetic-field-induced level crossings reveal two distinct S=1 excited states in the luminescence of 6H SiC containing titanium. Resolved structure on the lines is interpreted as an unusally large isotope effect, the zero field splitting D changing $\text{～}\text{1}\text{2}\text{\%}$ per unit atomic mass change for the five naturally occuring titanium isotopes. The sharp level crossings result from cross relaxation between one of these excited triplet states and other spin systems.     

Heat capacity of a five-coordinated ferromagnet,chloro bis(N,N-diethyldithiocarbamato)iron(III), in the temperature range from 0.4 to 20 K

The heat capacity of polycrystalline Fe[S₂CN(C₂H₅)₂]₂Cl has been measured in the temperature range from 0.411 to 19.55 K. The transition between ferromagnetic and paramagnetic states is characterized by a sharp λ-type anomaly centered at the Curie temperature, T_c = 2.412 ± 0.008 K. The enthalpy and the entropy of transition are 40.475 J mol^?1 and 11.199 J K^?1mol^?1 (= 1.347 R), respectively. The transition entropy is only 2.81% smaller than R In 4. This fact ascertains that the spin manifold is really a quartet. The ground spin states of the present compound are characterized by a zero-field splitting of the $\text{S =}\text{3}\text{2}$ state into two Kramers' doublets. The overlapping non-cooperative Schottky-type anomaly due to the energy separation between the two Kramers' doublets is separated tentatively from the cooperative heat capacity due to the exchange interaction. Based on a careful analysis of the transition entropy it may be concluded that the magnetic structure of the present complex would be a two-dimensional triangular Ising lattice. The exchange and the Curie-Weiss constants are also determined to be 0.155 and 4.19 K, respectively.     

Decoupled bands in odd-mass mercury isotopes

The schemes of the low-lying high-spin states in mercury isotopes with A = 195, 197, and 199 have been studied by γ-ray spectroscopy following (α, xn) reactions on separated platinum targets. Two bands have been excited in each Hg nucleus, one with positive parity based on the isomeric i$\text{13}\text{2}$. state and one, probably with negative parity, starting at spin $\text{case21}\text{2}$. The positive-parity states are interpreted with the rotation-aligned coupling scheme as decoupled bands; this implies oblate deformation in these three Hg isotopes. The negative-parity states are discussed as a decoupled i$\text{13}\text{2}$ neutron state coupled to the 5^?, 7^?, 9^?,…states, recently discovered in doubly even mercury isotopes.     

The spectrum of HeNe+

Discharges through mixtures of helium and neon show two band groups near 4250 and 4100 Å as first observed by Druyvesteyn. These bands, assigned to the HeNe⁺ ion by Tanaka, Yoshino, and Freeman, have been studied under high resolution and have been fairly completely analyzed. The upper state of the transition is a very weakly bound state resulting from $\text{He}{}^{\mathrm{+}}\text{(}{}^2\text{S) +}\text{Ne}\text{(}{}^1\text{S}{}_0\text{)}$. There are two lower states resulting from the two components of $\text{Ne}{}^{\mathrm{+}}\text{(}{}^2\text{P) +}\text{He}\text{(}{}^1\text{S}{}_0\text{)}$. The upper of these two (${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) is also very weakly bound while the lower of the two, the ²Σ⁺ ground state, has a dissociation energy of 0.69 eV and an r_e value of 1.30 Å. All bands in both band groups show four branches designated R_ff, Q_ef, Q_fe, and P_ee. From their analysis the rotational constants in the various vibrational levels of the three electronic states have been determined. While no spin splitting in the B²Σ⁺ state has been found the ground state X²Σ shows a very large spin splitting and the $\text{A}{}_2{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state a very large $\text{Ω-type}$ doubling. The vibrational numberings in all these states were established by the study of the spectrum of ³HeNe⁺. At the same time the hyperfine structure observed in all lines of ³HeNe⁺ confirmed the nature of the upper state B²Σ⁺ as resulting from He⁺ + Ne, i.e., by charge exchange from the ground state. The ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ component of the ²Π state has not been observed, presumably because of low intensity.     

Fine and hyperfine structure in three low-lying 3Σ+ states of molecular hydrogen

The fine structure constant (electron spin-spin coupling) and the hyperfine structure parameters (electron-nuclear spin coupling, including spin-rotation and electron-nuclear quadrupole coupling) in the low-lying triplet states b³Σ⁺ _u, a³Σ⁺ _g and e³Σ⁺ _u of molecular hydrogen and deuterium are calculated using a recently developed technique with full configuration interaction and multiconfiguration self-consistent field wave functions. The second-order spin-orbit coupling contribution to the ³Σ⁺ states splitting is negligible, and the calculations therefore provide a good estimate of the zero-field splitting based only on the electron spin-spin coupling values. For the bound a³Σ⁺ _g state a negligible zero-field splitting is found, in qualitative agreement with the e-a spectrum. The zero-field splitting parameter is considerable for the repulsive b³Σ⁺ _u state (?1 cm^?1) and of intermediate size for the bound e³Σ⁺ _u state. The isotropic hyperfine coupling constant is very large not only for the valence b³Σ⁺ _u state (1580 MHz) but also for the Rydberg a and e triplet states (?1400 MHz). The quadrupole coupling constants for the deuterium isotopes are negligible (0.04–0.07 MHz) for all studied triplet states. The electric dipole activity of the spin sublevels in the triplet-singlet transitions to the ground state is estimated by means of the quadratic response technique.     

Heat capacity of a five-coordinated iron(III) complex,chlorobis(N,N-dimethyldithiocarbamato) iron(III), between 0.4 and 300 k: New finding of a magnetic phase transition

The heat capacity of the title complex, Fe[S₂CN(CH₃)₂]₂Cl, has been measured between 0.4 and 300 K. A λ -type phase transition with a small shoulder arising from magnetic ordering was found at (0.609 ± 0.005) K. The character of the ordered phase has been suggested to be ferromagnetic on the basis of comparison between the methyl- and ethyl-homologues. The magnetic hyperfine structure of the Mössbauer spectra and the line broadening due to electronic relaxation effects at 1.2 K hitherto reported are concluded to result from a critical slowing-down when the magnetic transition temperature is approached from the high-temperature side. A Schottky-type anomaly arising from the zero-field splitting of a single ferric ion was observed around 2 K. The excess entropy beyond the lattice contribution at low temperatures amounts to (14.05 ±0.27) J K^?1mol^?1, which cannot be accounted for solely by the magnetic entropy of Rln 4 (= 11.53 JK^?1mol^?1) for the intermediate spin of $\text{S =}\text{3}\text{2}$. Two possibilities concerning additional conntribution have been discussed; one is a mixing of spin species of $\text{S =}\text{5}\text{2}$ and the other is a tunnel-splitting of the rotational levels of four methyl-constituents. The present study cannot give a definite conclusion as to the existence of dimeric units suggested from Mössbauer spectroscopy.     

Correspondences of the vibrational frequencies of the ground and electronic excited states of quinoxaline as revealed by the Raman intensities

The intensities of the Raman lines of quinoxaline were measured at different excitation wavelengths. The matrix element ratios of the vibronic couplings between the two lowest electronic excited states of the molecule were evaluated from the Raman intensities of the b₁ vibrations, and they were compared with the matrix element ratios obtained from the vibrational frequencies of the ground and electronic excited states of the molecule. It was suggested that the ground state frequency of the b₁ vibration at 867 cm^?1 decreases greatly to 425 cm^?1 in the lowest $\text{nπ}{}^1$ excited state.     

Heat capacity of a five-coordinated iron(III) complex,iodobis (N,N-Dimethyldithiocarbamato) iron(III), between 0.4 and 300 K

The heat capacity of iodobis (N, N-dimethyldithiocarbamato)iron(III) has been measured between 0.4 and 300 K. Based on the heat capacity and entropy at low temperatures it was found that the present sample consists of a mixture of monomer (ca. 40%) and dinier (ca. 60%); the former brings about a λ-type phase transition from an antiferromagnetic to a paramagnetic state at T_N = (1.65 ±0.04) K while the latter exhibits a Schottky-ype anomaly due to antiferromagnetic dimeric coupling, the effect of which becomes dominant below ca. 0.7 K. The zero-field splitting parameter of a single ferric ion was estimated to be $\text{D}\text{k}\text{=}\text{D}{}_{\mathrm{D}}\text{k}\text{= 14 K}$ for the monometer and the dimer, while the dimeric coupling constant was $\text{J}{}_{\mathrm{D}}\text{k}\text{= ?0.15 K}$. The entropy at low temperatures cannot be accounted for solely by the spin manifold. Additional contribution from a tunnel-splitting of the rotational levels of four constituent methyl-groups has been discussed. In this case, the level splitting of the ground state is 2.5 J mol^?1 and the barrier height of hindering potential is 2.3 kJ mol^?1.     

Coulomb excitation of 115Sn

Coulomb excitation of the nucleus ¹¹⁵Sn was studied with beams of ⁴He and ¹⁶O. Level energies, spins, mean-lives and B(E2) and B(M1) transition probabilities were obtained. Spin $\text{3}\text{2}$⁺ states were observed at 497.35 and 1280.08 keV and spin $\text{5}\text{2}$⁺ states were observed at 986.54 and 1416.78 keV. A state of 612.79 keV was observed to be indirectly excited by decay of the Coulomb excited states. Eleven B(E2) values and nine B(M1) values were obtained for the transitions between the low-lying states. In contrast to previous particle transfer results which suggested a clear distinction between shell-model and collective $\text{3}\text{2}$⁺ and $\text{5}\text{2}$⁺ states, our results suggest the collective strength is shared by the two $\text{3}\text{2}$⁺ and two $\text{5}\text{2}$⁺ states.     

Rotational analysis of a red A′ 2Σ+-X 2Πi system of CuO

High dispersion rotational analysis of a red CuO band system has led to the identification of an $\text{A′}{}^2\text{Σ}{}^{\mathrm{+}}\text{-X}{}^2\text{Π}{}_{\mathrm{i}}$ transition. The anomalous appearance of the branches is due to a very large spin splitting of the ²Σ upper state. The influence of centrifugal distortion effects on this spin splitting (γ_D and γ_H parameters) is essential for explaining the band structure. A reassignment of electronic symmetries of all the ²Σ states of CuO is proposed.     

Specific heat of Ni(ClO4)26H2O between 2 and 17 K

A specific heat investigation of nickel perchlorate hexahydrate was performed between 2 and 17 K. Lattice vibration and magnetic contributions were separated. The lattice term obeys a Debye αT³ law, with $\text{α = 4.04 × 10}{}^{\mathrm{?3}}\text{J}\text{K}{}^4$ mol. The magnetic contribution comes from the splitting of the ground state triplet of the Ni²⁺ ions, by axial and rhombic crystal field distortions, which can be explained by a Schottky specific heat with D = 1.72 KandE = 0.06 K.     

The uv spectrum of 18OD

The combined high-resolution ultraviolet (uv) absorption spectrum of ¹⁶OD and ¹⁸OD was obtained. State selective measurements of the transitions from the electronic ground state to the first excited electronic state, $\text{A}\text{?}{}^2\text{Σ}{}^{\mathrm{+}}\text{←}\text{X}\text{?}{}^2\text{Π}$, in the 0-0 vibronic band were performed by means of a narrow bandwidth dye laser system. Evaluation of these transition frequencies in wave-numbers yielded molecular constants as well as rotational term values for each of the isotopic species. A computer program based on a linearized least-squares procedure was used to determine the molecular constants and term values. The term value formulas which were employed for this purpose, take into account the Λ splitting and the centrifugal distortion of the diatomic species. The transitions, recalculated from the semiempirically determined term values agree with the measured absorption lines to better than 0.1 cm^?1. The following molecular constants are reported: B, D, H, the rotational constants of the ²Π and ²Σ⁺ states; O₀, P₀, Q₀, the constants of the Λ splitting of the ²Π state; A and A₁; the constants of the spin-orbit coupling of the ²Π state; and γ₀, the constant of the p doubling of the ²Σ⁺ state. Futhermore, term values up to J″ and J′ of 25.5 and the corresponding uv transitions are given.     

Laser spectroscopy of FeO: Rotational analysis of some subbands of the orange system

Extensive laser excitation spectra and rotationally resolved laser-induced fluorescence spectra have been recorded for the “orange system” of gaseous FeO in the wavelength regions 5790–6140 and 5580–5640 Å. Detailed rotational analyses have been performed for about $\text{20}\text{Ω}\text{′}$ substates lying between 16 350 and 18 550 cm^?1. These are found to comprise a very severely perturbed ⁵Δ_i excited electronic state with a bond length of about 1.69 Å (which is responsible for the parallel polarization of the electronic transition from the ⁵Δ_i ground electronic state) and a large number of “extra” $\text{Ω}$ substates with B′ values ranging from 0.38 to 0.50 cm^?1, which almost certainly belong to high vibrational levels of lower-lying electronic states. Evidence about the natures of the “extra” states is confusing, however, with the ⁵⁴FeO⁵⁶FeO isotope shifts apparently being in conflict with the patterns of vibrationally resolved laser-induced fluorescence. Every single $\text{Ω}$ substate that has been analyzed shows rotational perturbations of varying severity. The density and magnitude of the rotational perturbations are quite exceptional for a diatomic molecule, and result in a new type of totally chaotic diatomic spectrum. There is a remarkable similarity to the visible spectrum of NO₂: in NO₂ the complications arise from the high density of perturbing ground state vibrational levels; in FeO there is a correspondingly high density of perturbing electronic states at lower energy. The great complexity of the FeO spectrum arises because the states are in an awkward intermediate spin-coupling case which still resembles Hund's case (a) but shows strong tendencies toward Hund's case (c) coupling.     

Electron spin resonance spectra of two naturally occurring paramagnetic centres in diamond

A centre, characterised by an isotropie singlet at g = 2.000 and satellite lines having the correct relative intensity for ²⁹Si hyperfine features, has been detected in natural diamond. The form of the ²⁹Si hyperfine tensor suggests that the electronic structure of this silicon centre is similar to that of the common nitrogen centre. Although silicon is an expected impurity in diamond, paramagnetic centres containing it have not previously been reported. We have also detected the paramagnetic nitrogen centre previously reported, characterised by a hyperfine triplet with $\text{A}{}_6\text{(}{}^{14}\text{N) = 7.5G}$ and $\text{A}{}_{\mathrm{\perp }}\text{(}{}^{14}\text{N) = 5.0 G}$. This centre was accompanied by the common nitrogen centre in only one case. Other naturally occurring centres, apparently comprising two weakly coupled electrons in triplet states, were too poorly defined to characterise fully.     

Electronic transition moments between excited singlet states of the H2 molecule

The twelve transition moments which connect each of the three ¹Σ_g⁺ states EF, GK, and $\text{H}\text{H}$ with the three ¹Σ_u⁺ states B,B′, $\text{B″}\text{B}$ and with the state C¹Π_u were computed in the range of internuclear distances 1.25 ≤ R ≤ 15 a.u. using accurate electronic wavefunctions. The relative phases of the wavefunctions, which determine the signs of the transition moments, were consistently defined at all R values. The strong R dependences of the transition moments reflect the R-dependent changes in electronic character of the states involved in these transitions. At large R values the ¹Σ_g⁺-¹Σ_u⁺ transition moments are dominated by the two-electron charge resonance in the ionic configuration H⁺ + H^? whose transition moment is $\text{M(R) ? R}$.