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Physica Scripta

Energy transfer, collisional quenching and natural lifetime of laser-excitedD1Π state of the NaRb molecule

Mārtiņš Jansons, Janis Klavins, Zh Kharcheva, M. Tamanis

Published Apr 1, 1992• 4 citations
Publisher

Abstract

NaRb molecules in a thermal cell in a mixture of Na-Rb were excited to the D 1 Π state by means of a 514.5 nm beam from an Ar + laser. The natural lifetime for the NaRb D 1 Π, v' = 0, J' = 44 state, populated by the selective laser excitation, was found to be τ = 22.6 ± 1.8 ns. The kinetics of the molecular fluorescence lines as a function of the Rb atom concentration were also studied. The rate constant for collisional quenching of this molecular level by Rb atoms could be determined to k q = 2.1 · 10 −9 cm 3 s −1 . The experiments at steady state conditions demonstrate that energy transfer to the atomic 4 2 D levels of Rb dominates the collisional quenching with a rate constant of k ET = 1.2 · 10 −9 cm 3 s −1 . The results suggest that such molecule-atom transfer of electronic energy can be used to efficiently populate 2 D levels of alkali metal atoms.

DOI
10.1088/0031-8949/45/4/007

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Collisional Energy Transfer for Rb_2 in Excited State by Rb Atoms

Yifan Shen

At different Rb densities,Rb vapor was irradiated in a glass fluorescence cell with pulses of radiation from a pumped-laser,populating Rb 2 (B 1 Π u)state by single-photon absorption.Energy transfer in Rb 2 (B 1 Π u) + Rb(5S) collision is studied using methods of atomic and molecular fluorescence.The decay signal of time-resolved fluorescence from B 1 Π u → X 1 Σ + g transition was monitored.The effective lifetimes of the B 1 Π u state can be resolved.The plot of reciprocal of effective lifetimes of the B 1 Π u state against Rb densities yielded the slope that indicated the total cross section for deactivation and the intercept that provided the radiative lifetime of the state.The radiative lifetime 23.5ns for the B 1 Π u is obtained.The cross section for deactivation of the Rb 2 (B 1 Π u) molecules by collisions with Rb atoms is σ 3=(4.33 ± 0.14) × 10-15 cm 2.At the different Rb densities,the time-integrated intensities of the resulting Rb emission lines.I(5P 3/2 → 5S 1/2) and I(5P 1/2 → 5S 1/2) were measured.The absolute values for Rb 2 (B 1 Π u)+Rb→ Rb 2 (1 1 Σ + g) + Rb(5P J)collisional transfer cross sections have been obtained.The cross sections are σ 31=(2.86 ± 0.13) × 10-16 cm 2 (for transferring to 5P 1/2) and σ 32=(8.30 ± 0.38) × 10-16 cm 2 (for transferring to 5P 3/2),respectively.

Shinjang dashösi ilmiy jurnili•Jan 1, 2010•0 citations

Collisional quenching and radiation trapping kinetics for Rb(5p) in the presence of ethane

David A. Hostutler, Gordon D. Hager, Michael C. Heaven

Optically pumped alkali vapor lasers have been constructed using excitation of the D2 line (2P3/2-2S1/2) followed by lasing on the D1 line (2P1/2-2S1/2). Collisional relaxation is used to transfer population from 2P3/2 to the 2P1/2 level. The collision partner used for this step must have a large cross section for inducing transfer between the 2PJ levels, combined with a very small cross section for electronic quenching of the form M(2PJ)+Q→M(2S1/2)+Q (where M is an alkali metal and Q is the energy transfer agent). Ethane has proved to be an effective energy transfer agent for optically pumped Rb and Cs lasers. However, modeling of data for the Rb/C2H6 laser with the literature value for the quenching rate constant was unsuccessful. We have reexamined the quenching of Rb(2PJ) by C2H6 using time-resolved fluorescence techniques. Radiation trapping was significant under the conditions of our measurements, and an analysis of the interplay between the kinetics of trapping and quenching was carried out. It was found that quenching of Rb(2PJ) by C2H6 was very inefficient. The upper bound established for the quenching cross section was two orders of magnitude lower than that indicated by the previous determination.

Proceedings of SPIE, the International Society for Optical Engineering/Proceedings of SPIE•May 8, 2008•7 citations

Excitation energy transfer of the Rb 5P_J states induced by collisions with Ne atoms and N_2 molecules

YA Senjan

The collisional energy transfer process Rb(5PJ) +M,where M=Ne,N2 under gas cell conditions has been investigated.The Rb(5P3/2) state was excited by a diode laser.The direct 5P3/2→5S1/2 fluorescence and the sensitized 5P1/2→5S1/2 fluorescence as a function of quenching gas pressure had been measured.For collision with Ne where only electronic to translational energy transfer is possible.However,in the N2 case,electronics to vibrational or rotational transfer is important.Using a two-state rate equation model the transfer rate coefficients from Rb(5PJ) had been obtained.The rate coefficient for 5P3/2→5P1/2 transfer in collision with Ne is 1.53×10-12 cm3s-1.By comparing the relative fluorescence intensities for Ne and N2 case,and fitting the experimental results to the rate equation analysis,we estimate that the rate coefficient for 5P3/2→5P1/2 transfer in collision with N2 is 1.05×10-10cm3s-1.The quenching rate coefficient out of the 5PJ state is 1.12×10-10 cm3s-1.The results are discussed in relation to those of other experiments.

Jiguang zazhi•Jan 1, 2007•0 citations

Rb(5P_J)+(Ne, N_2) collisional energy transfer

Qing Wang

The collisional energy transfer in Rb(5P_J)+M collisions,where M=Ne,N_2 under gas cell conditions was investigated.For collision with Ne only electronic to translational energy transfer is possible.However,in the N_2 case,electronics to vibrational or rotational transfer is important.The Rb(5P_(3/2))state is excited by a tunable CW diode laser,where the laser is tuned slightly off resonance.The ratio of 5P_(1/2)→5S_(1/2)to the 5P_(3/2)→5S_(1/2) fluorescence as a function of quenching gas pressure was measured.Using a two-state rate equation model the transfer rate coefficients from the Rb(5P_J)state was obtained.The rate coefficient for 5P_(3/2)→5P_(1/2) transfer in collision with Ne is 1.53×10~(-12)cm~3s~(-1).Using the ratio of the 5P_(1/2) to 5P_(3/2) fluorescence for Ne and N_2 case,and fitting the experimental results to the rate equation analysis,we estimate that the rate coefficient for 5P_(3/2)→5P_(1/2) transfer in collision with N_2 is 8.83×10~(-11) cm~3s~(-1).The quenching rate coefficient of the 5P_J state is 1.25×10~(-10) cm~3s~(-1).A qualitative explanation for the results was given.

Chinese Journal of Quantum Electronics•Jan 1, 2007•0 citations

C'oUisional population of rubidium 4D and 65 levels by laser excitation of Rb and Rb-Na vapor mixture

Ya. P. Klyavinsh, Semyon Papernov, M. L. Yanson

The population and deactivation processes of the first excited 2S and 2D levels of alkali atoms have not been the focus of extensive attention to date, since these levels do not have dipole transitions to the 2S ground state, and the only radiative transitions to the 2p resonance level lie in the IR ( 1-3 fLm). We have demonstrated that in the case of potassium it is possible to populate the 32D and 52S levels in socalled optical collisions by laser excitation of the vapor and also by excitation energy transfer (EET) from the laser-excited Kidimers. 1 The lines of the corresponding 4D--->5P (1.529/1.475 f.lm and 6S ---> 5P (1.367/1.324 f.lm) transitions have also been identified in the laser-induced fluorescence of rubidium vapor,2 although the population mechanism of the levels is not examined in the present study. This st~dy will focus on determining the processes that result in the population of the Rb 42D and 62S levels and to determining the rate constants of these1'rocesses. The spectrum of the LGN-402 argon laser-induced fluorescence of Rb vapors was recorded in the IR by cooled Ge photo diodes selected for IR sensitivity and configured along the outlet slit of an MDR-3 monochromator. The synchronous detection method was employed. A FEU-79 photomultiplier was used in the visible range. Details on the experimental setup can be found in Ref. 3. The Rb vapor was excited by various argon laser lines (514.5-476.5 nm), although the 5l4.5-nm line was of primary interest. The C 1 ITu state of the RB2 dimer is not populated by this laser line; its predissociation efficiently populates the 52P resonance levels4 (see Fig. 1). Moreover the 5l4.5-nm laser line is closer in energy to the Rb 5S--->4D quadrupole transition (M= 75 cm-I). In the experiment at an atomic concentration [Rb] _1016 cm-3 the fluorescence lines from the 62S level (2.5 eV) were weaker by a factor of 50 compared to the lines from the 42D level (2.4 eV). A transition to the shorterwavelength laser excitation lines causes a certain increase in the population efficiency of the 4D level, although it also results in a more rapid growth of the population of the 5P resonance level due to the predissociation of Rb2 (C 1IT u ). I. In pure Rb vapors I) the line intensity of the 4D---> 5P transition has a linear relation to the laser excitation power ,(514.5 nm andp 5X 1016 cm-3 can be attributed to the onset of collisional quenching of the RB 4D state ('Trad =90 nsec). 5 So-called opticaJ.collisions lead to the population of the 4D level in these conditions (Aexc = 514.5 nm and no Na impurities)

OptSp•Aug 1, 1988•0 citations

[Mixing and quenching of Rb 5PJ states induced by collisions with He atoms and N2 molecules].

Fanxin Meng, Qin Chen, Kang Dai +1 more

The collisional energy transfer process Rb(5PJ)+M, where M= He, N2, under gas cell conditions has been investigated. The Rb(5P3/2) state was excited by a diode laser. The direct 5P3/2-->5S1/2 fluorescence and the sensitized 5P1/2-->5S1/2 fluorescence as a function of quenching gas pressure were measured. The 5P3/2 and 5P1/2 states are separated by 238 cm(-1). The closest other states are >6500 cm(-1) or >28 KT. Neglect of these other states should be an excellent approximation. In the experiment the Rb density was 4.5 x 10(11) cm(-3). Using radiation trapping theory the effective radiative rate=Gammae5P3/2-->5S1/2 2.47 x 10(7) s(-1) was obtained. For quenching by He only electronic to translational energy transfer is possible. However, in the N2 case, electronic to vibrational or rotational transfer is important. The Rb(5P3/2) state is 13 cm(-1) lower than the N2[X'Sigmag+ (V= 5, J= 11)]state; this energy gap is near resonant. The authors have not attempted to directly observe this possible E-R quenching channel Using a two-state rate equation model the transfer rate coefficients from Rb(5PJ) were obtained. The rate coefficient (k21He) for 5P3/2-->5P1/2 transfer in collision with He is 2.61 x 10(-12) cm3 x s(-1). By comparing the direct and sensitized fluorescence intensities for He and N2 case, and fitting the experimental results to the rate equation analysis, the authors estimate that the rate coefficient (k21N2) for 5P3/2-5P1/2 transfer in collision with N2 is 2.36 x 10(-11) cm3 x s(-1). The E-V quenching rate coefficient (kN2) of the 5PJ state is 1.44 x 10(-10) cm3 x s(-1). The authors found find that the rate coefficient kN2 is about 6 times larger than the k21N2. The assumption that the Cs-N2 energy transfer occurs primarily in collinear collision geometry is supported. The results are discussed in relation to those of other experiments.

•Dec 1, 2007•0 citations
NaRb molecules in a thermal cell in a mixture of Na-Rb were excited to the D 1 Π state by means of a 514.5 nm beam from an Ar + laser. The natural lifetime for the NaRb D 1 Π, v' = 0, J' = 44 state, populated by the selective laser excitation, was found to be τ = 22.6 ± 1.8 ns. The kinetics of the molecular fluorescence lines as a function of the Rb atom concentration were also studied. The rate constant for collisional quenching of this molecular level by Rb atoms could be determined to k q = 2.1 · 10 −9 cm 3 s −1 . The experiments at steady state conditions demonstrate that energy transfer to the atomic 4 2 D levels of Rb dominates the collisional quenching with a rate constant of k ET = 1.2 · 10 −9 cm 3 s −1 . The results suggest that such molecule-atom transfer of electronic energy can be used to efficiently populate 2 D levels of alkali metal atoms.
At different Rb densities,Rb vapor was irradiated in a glass fluorescence cell with pulses of radiation from a pumped-laser,populating Rb 2 (B 1 Π u)state by single-photon absorption.Energy transfer in Rb 2 (B 1 Π u) + Rb(5S) collision is studied using methods of atomic and molecular fluorescence.The decay signal of time-resolved fluorescence from B 1 Π u → X 1 Σ + g transition was monitored.The effective lifetimes of the B 1 Π u state can be resolved.The plot of reciprocal of effective lifetimes of the B 1 Π u state against Rb densities yielded the slope that indicated the total cross section for deactivation and the intercept that provided the radiative lifetime of the state.The radiative lifetime 23.5ns for the B 1 Π u is obtained.The cross section for deactivation of the Rb 2 (B 1 Π u) molecules by collisions with Rb atoms is σ 3=(4.33 ± 0.14) × 10-15 cm 2.At the different Rb densities,the time-integrated intensities of the resulting Rb emission lines.I(5P 3/2 → 5S 1/2) and I(5P 1/2 → 5S 1/2) were measured.The absolute values for Rb 2 (B 1 Π u)+Rb→ Rb 2 (1 1 Σ + g) + Rb(5P J)collisional transfer cross sections have been obtained.The cross sections are σ 31=(2.86 ± 0.13) × 10-16 cm 2 (for transferring to 5P 1/2) and σ 32=(8.30 ± 0.38) × 10-16 cm 2 (for transferring to 5P 3/2),respectively.
Optically pumped alkali vapor lasers have been constructed using excitation of the D2 line (2P3/2-2S1/2) followed by lasing on the D1 line (2P1/2-2S1/2). Collisional relaxation is used to transfer population from 2P3/2 to the 2P1/2 level. The collision partner used for this step must have a large cross section for inducing transfer between the 2PJ levels, combined with a very small cross section for electronic quenching of the form M(2PJ)+Q→M(2S1/2)+Q (where M is an alkali metal and Q is the energy transfer agent). Ethane has proved to be an effective energy transfer agent for optically pumped Rb and Cs lasers. However, modeling of data for the Rb/C2H6 laser with the literature value for the quenching rate constant was unsuccessful. We have reexamined the quenching of Rb(2PJ) by C2H6 using time-resolved fluorescence techniques. Radiation trapping was significant under the conditions of our measurements, and an analysis of the interplay between the kinetics of trapping and quenching was carried out. It was found that quenching of Rb(2PJ) by C2H6 was very inefficient. The upper bound established for the quenching cross section was two orders of magnitude lower than that indicated by the previous determination.
The collisional energy transfer process Rb(5PJ) +M,where M=Ne,N2 under gas cell conditions has been investigated.The Rb(5P3/2) state was excited by a diode laser.The direct 5P3/2→5S1/2 fluorescence and the sensitized 5P1/2→5S1/2 fluorescence as a function of quenching gas pressure had been measured.For collision with Ne where only electronic to translational energy transfer is possible.However,in the N2 case,electronics to vibrational or rotational transfer is important.Using a two-state rate equation model the transfer rate coefficients from Rb(5PJ) had been obtained.The rate coefficient for 5P3/2→5P1/2 transfer in collision with Ne is 1.53×10-12 cm3s-1.By comparing the relative fluorescence intensities for Ne and N2 case,and fitting the experimental results to the rate equation analysis,we estimate that the rate coefficient for 5P3/2→5P1/2 transfer in collision with N2 is 1.05×10-10cm3s-1.The quenching rate coefficient out of the 5PJ state is 1.12×10-10 cm3s-1.The results are discussed in relation to those of other experiments.
The collisional energy transfer in Rb(5P_J)+M collisions,where M=Ne,N_2 under gas cell conditions was investigated.For collision with Ne only electronic to translational energy transfer is possible.However,in the N_2 case,electronics to vibrational or rotational transfer is important.The Rb(5P_(3/2))state is excited by a tunable CW diode laser,where the laser is tuned slightly off resonance.The ratio of 5P_(1/2)→5S_(1/2)to the 5P_(3/2)→5S_(1/2) fluorescence as a function of quenching gas pressure was measured.Using a two-state rate equation model the transfer rate coefficients from the Rb(5P_J)state was obtained.The rate coefficient for 5P_(3/2)→5P_(1/2) transfer in collision with Ne is 1.53×10~(-12)cm~3s~(-1).Using the ratio of the 5P_(1/2) to 5P_(3/2) fluorescence for Ne and N_2 case,and fitting the experimental results to the rate equation analysis,we estimate that the rate coefficient for 5P_(3/2)→5P_(1/2) transfer in collision with N_2 is 8.83×10~(-11) cm~3s~(-1).The quenching rate coefficient of the 5P_J state is 1.25×10~(-10) cm~3s~(-1).A qualitative explanation for the results was given.
The population and deactivation processes of the first excited 2S and 2D levels of alkali atoms have not been the focus of extensive attention to date, since these levels do not have dipole transitions to the 2S ground state, and the only radiative transitions to the 2p resonance level lie in the IR ( 1-3 fLm). We have demonstrated that in the case of potassium it is possible to populate the 32D and 52S levels in socalled optical collisions by laser excitation of the vapor and also by excitation energy transfer (EET) from the laser-excited Kidimers. 1 The lines of the corresponding 4D--->5P (1.529/1.475 f.lm and 6S ---> 5P (1.367/1.324 f.lm) transitions have also been identified in the laser-induced fluorescence of rubidium vapor,2 although the population mechanism of the levels is not examined in the present study. This st~dy will focus on determining the processes that result in the population of the Rb 42D and 62S levels and to determining the rate constants of these1'rocesses. The spectrum of the LGN-402 argon laser-induced fluorescence of Rb vapors was recorded in the IR by cooled Ge photo diodes selected for IR sensitivity and configured along the outlet slit of an MDR-3 monochromator. The synchronous detection method was employed. A FEU-79 photomultiplier was used in the visible range. Details on the experimental setup can be found in Ref. 3. The Rb vapor was excited by various argon laser lines (514.5-476.5 nm), although the 5l4.5-nm line was of primary interest. The C 1 ITu state of the RB2 dimer is not populated by this laser line; its predissociation efficiently populates the 52P resonance levels4 (see Fig. 1). Moreover the 5l4.5-nm laser line is closer in energy to the Rb 5S--->4D quadrupole transition (M= 75 cm-I). In the experiment at an atomic concentration [Rb] _1016 cm-3 the fluorescence lines from the 62S level (2.5 eV) were weaker by a factor of 50 compared to the lines from the 42D level (2.4 eV). A transition to the shorterwavelength laser excitation lines causes a certain increase in the population efficiency of the 4D level, although it also results in a more rapid growth of the population of the 5P resonance level due to the predissociation of Rb2 (C 1IT u ). I. In pure Rb vapors I) the line intensity of the 4D---> 5P transition has a linear relation to the laser excitation power ,(514.5 nm andp 5X 1016 cm-3 can be attributed to the onset of collisional quenching of the RB 4D state ('Trad =90 nsec). 5 So-called opticaJ.collisions lead to the population of the 4D level in these conditions (Aexc = 514.5 nm and no Na impurities)
The collisional energy transfer process Rb(5PJ)+M, where M= He, N2, under gas cell conditions has been investigated. The Rb(5P3/2) state was excited by a diode laser. The direct 5P3/2-->5S1/2 fluorescence and the sensitized 5P1/2-->5S1/2 fluorescence as a function of quenching gas pressure were measured. The 5P3/2 and 5P1/2 states are separated by 238 cm(-1). The closest other states are >6500 cm(-1) or >28 KT. Neglect of these other states should be an excellent approximation. In the experiment the Rb density was 4.5 x 10(11) cm(-3). Using radiation trapping theory the effective radiative rate=Gammae5P3/2-->5S1/2 2.47 x 10(7) s(-1) was obtained. For quenching by He only electronic to translational energy transfer is possible. However, in the N2 case, electronic to vibrational or rotational transfer is important. The Rb(5P3/2) state is 13 cm(-1) lower than the N2[X'Sigmag+ (V= 5, J= 11)]state; this energy gap is near resonant. The authors have not attempted to directly observe this possible E-R quenching channel Using a two-state rate equation model the transfer rate coefficients from Rb(5PJ) were obtained. The rate coefficient (k21He) for 5P3/2-->5P1/2 transfer in collision with He is 2.61 x 10(-12) cm3 x s(-1). By comparing the direct and sensitized fluorescence intensities for He and N2 case, and fitting the experimental results to the rate equation analysis, the authors estimate that the rate coefficient (k21N2) for 5P3/2-5P1/2 transfer in collision with N2 is 2.36 x 10(-11) cm3 x s(-1). The E-V quenching rate coefficient (kN2) of the 5PJ state is 1.44 x 10(-10) cm3 x s(-1). The authors found find that the rate coefficient kN2 is about 6 times larger than the k21N2. The assumption that the Cs-N2 energy transfer occurs primarily in collinear collision geometry is supported. The results are discussed in relation to those of other experiments.