Photo-Induced Electron Spin Polarization in Chemical and Biological Reactions: Probing Structure and Dynamics of Transient Intermediates by Multifrequency EPR Spectroscopy

In this minireview, modern multifrequency electron paramagnetic resonance (EPR) spectroscopy, in particular, at high magnetic fields, is shown to provide detailed information about structure, motional dynamics and spin chemistry of transient radicals and radical pairs occurring in photochemical reactions. Examples discussed comprise spin-polarized radicals and radical pairs in disordered systems, such as ultraviolet-irradiated quinone and ketone compounds in fluid alcohol solutions, green-light initiated electron transfer in biomimetic porphyrin?Cquinone donor?Cacceptor model systems in frozen solution, aiming at artificial photosynthesis, and red-light initiated electron transfer in natural photosynthetic reaction-center protein complexes. The transient paramagnetic states exhibit characteristic electron polarization (CIDEP) effects originating from a triplet mechanism, a radical-pair mechanism or a correlated coupled radical-pair mechanism. They contain valuable information about structure and dynamics of the short-lived reaction intermediates. Moreover, the CIDEP effects can be exploited for signal enhancement. Continuous-wave and pulsed versions of time-resolved high-field EPR spectroscopy, such as transient EPR and electron spin-echo experiments, are compared with respect to their advantages and limitations for the specific photoreaction under study. Furthermore, orientation resolving W-band pulsed electron-electron double resonance (PELDOR) experiments on the spin-correlated coupled radical pair $ {\text{P}}_{865}^{ \cdot + } $ $ {\text{Q}}_{\text{A}}^{ \cdot - } $ in frozen solution reaction centers from the purple photosynthetic bacterium Rb. sphaeroides reveal details of distance and orientation of the pair partners in their charge-separated transient state. The results are compared with those of the ground-state P₈₆₅Q_A. In conjunction with Q-band proton electron-nuclear double resonance (ENDOR) experiments the W-band PELDOR results provide decisive evidence that the local structure of the Q_A binding site does not change under photoreduction of the quinone??in agreement with earlier FTIR studies. The examples given demonstrate that multifrequency EPR experiments on disordered systems add heavily to the capabilities of ??classical?? spectroscopic and diffraction techniques for determining structure?Cdynamics?Cfunction relations of biochemical processes, since short-lived intermediates can be observed in real time while staying in their working states at biologically relevant time scales.     

Oxidation of Pyrite Grains: A Mössbauer Spectroscopy and Mineral Magnetism Study

Fe²⁺ in pyrite is found in a low-spin d⁶ configuration, a necessary condition for diamagnetic and semi-conducting properties of material. The semi-conducting property of pyrite has been studied since the time when pyrite was used as a rectifier in early radios. Pyrite posses the highest possible crystal field stabilisation energy and offers a better altemative as solar material compared to Si-based materials. Unfortunately, pyrite is difficult to study due to its inherent deviation from stoichiometry and its ease of oxidation. Since pyrite and its oxidation products are all Fe-bearing phases, combining Mössbauer spectroscopy with mineral magnetic methods provides enough information to monitor the oxidation of pyrite in air and identify the different phases produced and their relation to different experimental parameters. For mm-sized grain samples, heating FeS₂ at temperatures between 450 °C and 650 °C five different mineral assemblages are identified. FeS₂ is oxidized to α-Fe₂O₃ along two separate routes: $${\text{FeS}}_{2} \to {\text{FeSO}}_{4} \to \varepsilon {\text{ - Fe}}_{2} {\text{O}}_{3} \to \alpha {\text{ - Fe}}_{2} {\text{O}}_{3} ;\;{\text{and}}$$ $${\text{FeS}}_{2} \to {\text{FeSO}}_{4} \to {\text{Fe}}_{2} {\left( {{\text{SO}}4} \right)}_{3} \to \beta {\text{ - Fe}}_{2} {\text{O}}_{3} \to \alpha {\text{ - Fe}}_{2} {\text{O}}_{3} $$      

Stability of {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} and {\text{SrZr}}_{{0.2}} {\text{Ce}}_{{0.7}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} under H2 atmospheres

Previous H₂ permeation tests showed a degradation of H₂ permeation flux with time. To understand the cause of degradation and develop a solution, the stability of $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ and $ {\text{SrZr}}_{{0.2}} {\text{Ce}}_{{0.7}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ samples were studied under dry and wet H₂ atmospheres. Total conductivity of $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ increased with time in dry H₂. The X-ray diffraction pattern of $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ after dry hydrogen atmosphere heat treatments show CeO₂ peaks indicating that $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ decomposes under dry H₂ atmospheres; scanning electron microscopy and energy dispersive X-ray spectroscopy analyses prove that decomposition proceeded along the grain boundaries. $ {\text{SrZr}}_{{0.2}} {\text{Ce}}_{{0.7}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ was investigated and demonstrated greater stability under dry hydrogen atmospheres. However, Zr substitution results in a tradeoff with electrical properties.     

A stable and easily sintering {\text{BaCe}}_{0.7} {\text{Sn}}_{0.1} {\text{Gd}}_{0.2} {\text{O}}_{3 - \delta } electrolyte for solid oxide fuel cells

${\text{BaCe}}_{0.7} {\text{Sn}}_{0.1} {\text{Gd}}_{0.2} {\text{O}}_{3 - \sigma } $ (BCSG) and ${\text{BaCe}}_{0.8} {\text{Gd}}_{0.2} {\text{O}}_{3 - \sigma } $ (BCG) powders were prepared by solid-state reaction method. After exposure in 5% CO₂?+?5% H₂O?+?90% N₂ at 500 °C for 5 h, the BCSG powders were hardly affected while the BCG powders decomposed into CeO₂ and BaCO₃ phases. Moreover, the relative density of BCSG reaches 97%, while the BCG just displays 91% after sintering at 1,400 °C. The BCSG displays a conductivity of 0.01 S/cm at 700 °C in humid hydrogen, which is quite close to 0.012 S/cm for BCG. A fuel cell with BCSG exhibits 1.02 V for open circuit voltage, 420 mW/cm² for peak performance and 0.23 Ω cm² for interfacial resistance at 700 °C, respectively.     

Electromagnetic moment investigation of two short-lived isomeric states in118Sb

Two short-lived isomeric states in¹¹⁸Sb have been investigated by the¹¹⁸Sn(p, n),¹¹⁸Sn(d, 2n) and¹¹⁵In(α, n) reactions. The TDPAD method on solid and liquid metallic targets was used to measure the electromagnetic moments of these states. The results of the experiments are: $$\begin{gathered} T_{1/2} = 13.4{\text{ }}(3){\text{ }}ns I^\pi = 3^ - {\text{ }}g = - 1.254(31){\text{ }}|Q| = 0.25{\text{ }}(5){\text{ }}b, \hfill \\ T_{1/2} = 22.8{\text{ }}(4){\text{ }}ns I^\pi = 7^ + {\text{ }}g = + 0.680(18){\text{ }}|Q| > 1.4{\text{ }}b. \hfill \\ \end{gathered}$$ Pure \([\pi 2d_{5/2} \otimes v1h_{1{\text{ }}1/2} ]_{3 - }\) and \([\pi 1g_{9/2}^{ - 1} \otimes v2d_{5/2}^{ - 1} ]_{7 + }\) configurations have been established for the two isomeric states. An experimental evidence concerning the participation of the 1g ₉ ^2/?1 proton shell-model intruder excitation into the positive parity low-lying level structure of the odd-odd¹¹⁸Sb nucleus was obtained.     

Electron paramagnetic resonance and spinlattice relaxation of Cu2+ ions in ZnSeO4·6H2O

In this paper, we present detailed studies of the EPR spectra of Cu²⁺ ions in single crystals of ZnSeO₄·6H₂O. We describe the spectrum with a rhombic spin Hamiltonian with the following parameters: g_z=2.427; g_y=2.095; g_x=2.097; A _z ⁶⁵ =138.4·10^?4 cm^?1; A _x ⁶⁵ =22.3·10^?4 cm^?1. We studied spin-lattice relaxation in the temperature range 4–300 K at the frequency v≈9.3 GHz. The measured spin-lattice relaxation rate for the orientation H∥L₄ is described well at T<5 K by a linear dependence, while at T>5 K it is described by the sum of three exponentials: $$T_1^{ - 1} = 0.27T + 3.3 \cdot 10^{\text{s}} \exp \left( {\frac{{ - 69.5}}{T}} \right) + 2.6 \cdot 10^7 \exp \left( {\frac{{ - 140}}{T}} \right) + 1.36 \cdot 10^{10} \exp \left( {\frac{{ - 735.6}}{T}} \right){\text{ sec}}^{{\text{ - 1}}} $$ .We discuss possible reasons for the exponential dependence of T ₁ ^?1 for the Raman process.     

Fast proton conduction path in {\text{Ni}} - {\text{BaCe}}_{{0.8}} {\text{Y}}_{{0.2}} {\text{O}}_{{2.9 - \delta }} membrane

The effect of metal-to-oxide grain boundary layer in $ {\text{Ni}} - {\text{BaCe}}_{{0.8}} {\text{Y}}_{{0.2}} {\text{O}}_{{3 - \delta }} $ (BCY) cermet membrane on hydrogen permeation was studied by applying the different size of oxide grain on Ni-BCY membranes. Two types of cermet membranes having different grain size of oxide were prepared by using different starting particle size of oxide powder. The hydrogen flux of coarse-oxide-grain membrane showed higher flux than that of small-oxide-grain membrane. It was understood that the negative potential at metal-to-oxide grain boundary, reference to the bulk oxide ( $ \phi _{0} < \phi _{\infty } = 0 $ ), was developed, and the accumulation of the effectively positively charged protons may occur at the grain boundary layer (space charge layer), which may result in providing highly conductive proton path by shifting the charge neutrality condition from $ {\left[ {OH^{ \bullet }_{O} } \right]} = {\left[ {Y^{/}_{{Ce}} } \right]} $ to $ {\left[ {OH^{ \bullet }_{O} } \right]} = n $ .     

Singular $$ \mathcal{R}$$ -Matrices and Drinfeld's Comultiplication

We compute the $\mathcal{R}$ -matrix which intertwines two dimensional evaluation representations with Drinfeld comultiplication for ${\text{U}}_q \left( {\widehat{{\text{sl}}}_{\text{2}} } \right)$ . This $\mathcal{R}$ -matrix contains terms proportional to the δ-function. We construct the algebra $A\left( \mathcal{R} \right)$ generated by the elements of the matrices L^±(z) with relations determined by $\mathcal{R}$ . In the category of highest-weight representations, there is a Hopf algebra isomorphism between $A\left( \mathcal{R} \right)$ and an extension $\overline {\text{U}} _q \left( {\widehat{{\text{sl}}}_{\text{2}} } \right)$ of Drinfeld's algebra.     

Study of the ion exchange equilibrium of Cl−, NO_3^{ - } , and SO_4^{{2 - }} ions on the AMX membrane

Equilibrium between the ion exchange membrane and solutions of anions at various valences has been the subject of this investigation. Competitive ion exchange reactions were studied on a strong base anion exchange membrane AMX manufactured by Tokuyama, commercialized by Eurodia, involving Cl^?, $ {\text NO}_3^{ - } $ and $ {\text SO}_4^{{2 - }} $ ions. Solution concentrations studied were 0.05 and 0.1 M for all the systems reported. Experiments were performed with sodium as the counter ion, and the temperature was kept constant (T?=?298 K). Ionic exchange isotherms for the binary systems— $ {{\text Cl}^{ - }}/{\text NO}_3^{ - } $ , $ {{\text Cl}^{ - }}/{\text SO}_4^{{2 - }} $ , and $ {\text NO}_3^{ - }/{\text SO}_4^{{2 - }} $ —were established. The obtained results show that the sulfate was the most strongly sorbed, and the selectivity order is $ {\text SO}_4^{{2 - }} > {\text NO}_3^{ - } > {{\text Cl}^{ - }} $ at 0.05 M and $ {\text NO}_3^{ - } > {\text SO}_4^{{2 - }} > {{\text Cl}^{ - }} $ at 0.1 M under the experimental conditions. Selectivity coefficients $ K_{{{{{\text Cl} }^{ - }}}}^{{{\text NO}_3^{ - }}} $ , $ K_{{2{{{\text Cl} }^{ - }}}}^{{{\text SO}_4^{{2 - }}}} $ , and $ K_{{2{\text NO}_3^{ - }}}^{{{\text SO}_4^{{2 - }}}} $ for the three binary systems were determined. All the results given by this membrane were compared with those obtained, in the same conditions, with the RPA membrane (produced by RHONE POULENC). Ternary equilibrium data were taken for $ {{\text Cl}^{ - }}/{\text NO}_3^{ - }/{\text SO}_4^{{2 - }} $ . The prediction of the ternary system based only on the binary data was consistent with the experimental data obtained for this system. The good agreement between the experimental and the predicted data showed that the proposed framework can be considered as an effective method to predict many ternary systems from binary systems.     

On the similarity solution of evolution equation u t =H(x,t, u,u x,u xx , ...)

Let $$\begin{gathered} u^* = u + \in \eta (x,{\text{ }}t,{\text{ }}u), \hfill \\ \hfill \\ \hfill \\ x^* = x + \in \xi (x, t, u{\text{),}} \hfill \\ \hfill \\ \hfill \\ {\text{t}}^{\text{*}} = {\text{ }}t + \in \tau {\text{(}}x,{\text{ }}t,{\text{ }}u), \hfill \\ \end{gathered}$$ be an infinitesimal invariant transformation of the evolution equation u _t =H(x,t,u,?u/?x,...,? ⁿ :u/?x ⁿ . In this paper we give an explicit expression for \(\eta ^{X^i }\) in the ‘determining equation’ $$\eta ^T = \sum\limits_{i = 1}^n {{\text{ }}\eta ^{X^i } {\text{ }}\frac{{\partial H}}{{\partial u_i }} + \eta \frac{{\partial H}}{{\partial u_{} }} + \xi \frac{{\partial H}}{{\partial x}} + \tau } \frac{{\partial H}}{{\partial t}},$$ where u _i =? ⁱ u/?x ⁱ . By using this expression we derive a set of equations with η, ξ, τ as unknown functions and discuss in detail the cases of heat and KdV equations.     

Selectivity of anion exchange membrane modified with polyethyleneimine

Previous works have been made on the improvement of selectivity of ion exchange membranes using adsorption of polyelectrolyte on the surface of the materials. The modification of the surface material in the case of an anion exchange membrane concerns the hydrophilic/hydrophobic balance properties and its relationship with the hydration state. Starting from this goal, the AMX membrane has been modified, in this work, by adsorption of polyethyleneimine on its surface. Many conditions of modification of the AMX membrane surface were studied. A factorial experimental design was used for determining the influent parameters on the AMX membrane modification. The results obtained have shown that the initial concentration of polyethyleneimine and the pH of solution were the main influent parameters on the adsorption of polyethyleneimine on the membrane surface. Competitive ion exchange reactions were studied for the modified and the unmodified membrane involving $ {\text{C}}{{\text{l}}^{ - }} $ , $ {\text{NO}}_3^{ - } $ and $ {\text{SO}}_4^{{2 - }} $ ions. All experiments were carried out at constant concentration of 0.3?mol?L^?1 and at 25?°C. Ion exchange isotherms for the binary systems $ \left( {{\text{C}}{{\text{l}}^{ - }}/{\text{NO}}_3^{ - }} \right) $ , $ \left( {{\text{C}}{{\text{l}}^{ - }}/{\text{SO}}_4^{{2 - }}} \right) $ and $ \left( {{\text{NO}}_3^{ - }/{\text{SO}}_4^{{2 - }}} \right) $ were studied. The obtained results show that chloride was the most sorbed and the selectivity order both for the modified membrane and the unmodified one is: $ {\text{Cl}} > {\text{NO}}_3^{ - } > {\text{SO}}_4^{{2 - }} $ , under the experimental conditions. Selectivity coefficients $ {\text{K}}_{{{\text{C}}{{\text{l}}^{ - }}}}^{{{\text{NO}}_3^{ - }}} $ , $ {\text{K}}_{{2{\text{C}}{{\text{l}}^{ - }}}}^{{{\text{SO}}_4^{{2 - }}}} $ and $ {\text{K}}_{{2{\text{NO}}_3^{ - }}}^{{{\text{SO}}_4^{{2 - }}}} $ for the three binary systems and for the two membranes were determined. It was also observed that for the modified membrane the selectivity towards sulfate ion decrease and the modified membrane became more selective towards monovalent anions.     

Theoretical study of collision and collision-free radiative lifetimes of {{\text{S}}_2}\left( {{{\text{B}}^3}\Sigma_{\text{u}}^{-} \left( {{\upsilon^{\prime}} = 0 - 9} \right)} \right)

We calculate multireference configuration-interaction wavefunctions and the potential-energy curves for the $ {B^3}\Sigma_u^{-} $ and $ {X^3}\Sigma_g^{-} $ states of the collision-free S₂ molecule and the T-shape collision complex S₂?CHe using cc-pVQZ basis sets. We obtain the transition dipole moments of the $ {{\text{S}}_2}\left( {{B^3}\Sigma_u^{-} \to {X^3}\Sigma_g^{-} } \right) $ and the Franck?CCondon factors between the vibrational levels of this two states. We evaluate the radiative lifetimes of $ {{\text{S}}_2}\left( {{B^3}\Sigma_u^{-} \left( {{\upsilon^{\prime}} = 0 - 9} \right)} \right) $ levels of the collision complex and the collision-free molecule and compare them with the experiments. The collision provides little change in the radiative lifetimes of $ {{\text{S}}_2}\left( {{B^3}\Sigma_u^{-} \left( {{\upsilon^{\prime}} = 0 - 9} \right)} \right) $ according to the previous calculations. We obtain excellent agreement between the theoretical results and the experiments. The data calculated are very useful in the study of the microwave-driven high-pressure sulfur lamp and an S₂ laser pumped by a transverse fast discharge.     

Detection of a hexadecapole interaction in the atomic ground state3 H 6 of167Er

Using the atomic beam magnetic resonance method, precision measurements of the hyperfine structure and Zeeman interactions have been performed in the ground state 4f ¹²6s ^{2 3} H ₆ of¹⁶⁷Er. The experimental data were analyzed using an effective operator parametrized in the space of states of the ground state multiplet. It yielded eight effective hyperfine structure and Zeeman interaction constants which served to calculate the seven hyperfine separations of the ground state. The results are: $$\begin{gathered} 2F 2F' v_{FF'} (MHz) \hfill \\ 5 7 - 354.371 9409 (27) \hfill \\ 7 9 - 2{\text{78}}{\text{.231}} {\text{8263(14)}} \hfill \\ {\text{9}} 11 - 69.050 7785 (4) \hfill \\ 11 13 + 302.735 3731(12) \hfill \\ 13 15 + 866.691 3871(10) \hfill \\ 15 17 + 1,652.383 5154 (6) \hfill \\ 17 19 + 2,689.380 8050(10) \hfill \\ \end{gathered}$$ From the effective Zeeman interaction constants it was possible to determine an improvedg _I -value, uncorrected for atomic diamagnetism: $$ g_I = + 0.086 775 (19) \cdot 10^{ - 3}$$ Furthermore a hexadecapole interaction corresponding to a diagonal hexadecapole interaction constant $$A_4 = - 16 (10) Hz$$ could be established which is of the order of magnitude expected from Coulomb excitation experiments as well as theoretical calculations.     

Calculations of the Spin-Hamiltonian Parameters for the Trigonal Cr3+ and Mn4+ Centers in Ca3Ga2Ge3O12 (CGGG) Garnet Crystal

The spin-Hamiltonian parameters (zero-field splitting D, g-factors g _//, g _⊥ and hyperfine structure constants A _//, A _⊥) of Cr³⁺ and Mn⁴⁺ ions at the trigonal Ga³⁺ site of Ca₃Ga₂Ge₃O₁₂ (CGGG) garnet crystals are calculated from the high-order perturbation formulas based on the two-mechanism model. In the model, besides the contributions to spin-Hamiltonian parameters from the crystal-field (CF) mechanism in the frequently applied CF theory, those from the charge-transfer (CT) mechanism (which is neglected in CF theory) are taken into account. The calculated results are in reasonable agreement with the experimental values. The defect structures of Cr³⁺ and Mn⁴⁺ impurity centers in CGGG crystals are also obtained from the calculations. The calculations show that the relative importance of CF mechanism (characterized by $ \left| {{{Q^{\text{CT}} } \mathord{\left/ {\vphantom {{Q^{\text{CT}} } {Q^{\text{CF}} }}} \right. \kern-0pt} {Q^{\text{CF}} }}} \right| $ , where $ Q = D,\;\Delta g_{\rm{//}} ,\;\Delta g_{ \bot } ,\;A_{\rm{//}}^{(2)} or\;A_{ \bot }^{(2)} $ ) for Mn⁴⁺ center in CGGG is larger than that for Cr³⁺ center. So, for the high valence state dⁿ ions in crystals, the reasonable calculations of spin-Hamiltonian parameters should consider the contributions due to both the CF and CT mechanisms.     

Empirical two-point correlation functions

Let A ₁ , A ₂ , A ₃ A ₄ be four observables, the compatible observables among them being (A ₁ , A ₃ ), (A ₁ , A ₄ ), (A ₂ , A ₃ ), (A ₂ , A ₄ ). In order that the empirical data be reproducible by a quantum or a classical theory, the two-point correlation functions $$\{ C_{ij} = \left\langle {A_i A_j } \right\rangle :i,j a compatible pair\} $$ must necessarily satisfy $$|X_{13} X_{14} - X_{23} X_{24} | \leqslant \left( {1 - X_{13} ^2 } \right)^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} \left( {1 - X_{14} ^2 } \right)^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} + \left( {1 - X_{23} ^2 } \right)^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} \left( {1 - X_{24} ^2 } \right)^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} (*)$$ where X_ij=C_ijC _ii ^?1/2 C _jj ^?1/2 . In the case ofGaussian data, this inequality is alsosufficient; If (*) holds, there is a Gaussian joint distribution for A ₁ , A ₂ , A ₃ , A ₄ which reproduces the Gaussian data for compatible pairs. It follows that Bell's inequality is satisfied by all true-false propositions about the Gaussian data. A further consequence of the analysis is thatquantum Gaussian fields satisfy Bell's inequality for all true-false propositions aboutfield measurements. The maximum violation of (*) corresponds to Rastall's example in the case of two-valued observables.     

Electro-Production of Light Lambda Hypernuclei

Through the study of light hypernuclei, we can learn about hyperon nucleon interaction. The hypernuclear spectroscopy with electron beams is one of most powerful methods to study detailed structure of light hypernuclei thanks to its high energy resolution. With a decade of efforts at Jefferson Lab, the spectroscopy of Λ hypernuclei with an electron beam is now established. Observation of ${_{\Lambda}^{7}}$ He which gave the last missing binding energy of the A = 7, T = 1 iso-triplet hypernuclei provides an important experimental input for the charge symmetry breaking (CSB) effect of the ΛN interaction. Further study about A = 4 hypernuclear iso-doublet, ${_{\Lambda}^{4}}$ H and ${_{\Lambda}^{4}}$ He, is necessary and such experiments are now planned.     

Classical r-matrices and compatible Poisson brackets for coupled KdV systems

The formalism of classical r-matrices is used to construct families of compatible Poisson brackets for some nonlinear integrable systems connected with Virasoro algebras. We recover the coupled KdV [1] and Harry Dym [2] systems associated with the auxiliary linear problem 1 $$\sum\limits_{i = 0}^N {\lambda '\left( {a_i \frac{{{\text{d}}^{\text{2}} }}{{{\text{dx}}^2 }} + {\text{u}}_{\text{i}} } \right)} \psi = 0$$ .     

Femtosecond relaxation kinetics of highly excited \mathrm{M}_{\mathrm{Na}}^{**} states in CaF2 at 3.2 eV and 4.7 eV

Femtosecond (fs) laser pulses at variable delay times allowed us to track the fast non-radiative transitions between the manifold of highly excited $\mathrm{M}_{\mathrm{Na}}^{**}$ states to the lower lying fluorescent $\mathrm{M}_{\mathrm{Na}}^{*}$ state in CaF₂. Two distinct $\mathrm{M}_{\mathrm{Na}}^{**}$ states of the manifold at 3.16?eV ( $\mathrm{M}_{\mathrm{Na}2}^{**}$ ) and 4.73?eV ( $\mathrm{M}_{\mathrm{Na}3}^{**}$ ) were populated using the second (SH) and third harmonics (TH) of fs laser light at 785?nm. The population kinetics of the fluorescent $\mathrm{M}_{\mathrm{Na}}^{*}$ state in the 2?eV excitation energy range was revealed by depleting its fluorescence centered at 740?nm using fundamental near infrared (NIR) fs laser pulses. The related time constants for $\mathrm{M}_{\mathrm{Na}2,3}^{**}{\sim}{>} \mathrm{M}_{\mathrm{Na}}^{*}$ relaxation amounted to 1.0±0.14?ps and 3.0±0.3?ps upon SH and TH excitation, respectively.