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.
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.
Rb vapor was irradiated in a glass fluorescence cell with pulses of radiation from a YAG laserpumped OPO laser,populating 5D_j(or 7S) state by two-photon absorption.Energy transfer in Rb (5D_J,7S)+Rb(5S) collision is studied using methods of atomic fluorescence.The resulting fluorescence includes a direct component emitted in the optically excited state decay and a sensitized component arsing. from the collisional populated state.At the different densities of the components,fitting a three-state rate equation model,the cross sectionσ=(3.7±0.9)×10~(-14) cm~2 was obtained for Rb(5D_(5/2))→Rb(5D_(3/2)) transfer.The cross section for excitation transfer out of the 5D_J doublet are(3.1±1.2)×10~(-14) cm~2(for J = 5/2) and(2.0±0.6)×10~(-14) cm~2(for J = 3/2),respectively.The energy transfer cross section for the Rb(5D)→Rb(7S) is small,(1.6±0.4)×10~(-16) cm~2.The 5D_J state is quenched mainly in the reverse energy pooling processes,i.e.Rb(5D_J)+Rb(5S)→Rb(5P)+ Rb(5P).
Using a YAG-laser pumped OPO laser excite the pure rubidium cell,the Rb2(1Σg) state was excited to Rb2(1Λg) state,the temperature controlled between 519-548K while Rb atomic density ranged 4-8×1015cm-3 and Rb2 density was about 1014cm-3.The fluorescence spectrum of cesium vapor was used to study predissociation and transfer collision.From time-resolved fluorescence for the 1Λg →B1Πu transition at different Rb densities,the effective lifetimes of the 1Λg state could obtain.Based on the Stern-Volmer equation,the sum of the radiative and predissociative rates and the total cross section for deactivation of the Rb2(1Λg) were from the slope and the intercept,due to a linear relationship between the effective lifetime reciprocals and Rb densities.The time-integrated intensities of I3[Rb2(1Λg→B1Πu)],I2[Rb(8S→5P3/2)]and I1[Rb(6D→5P3/2)] were measured by photon counter.By combining the slope and the intercept with the result obtained by the Stern-Volmer equation,we obtain predissociative rates ΓP8S=(6.5±0.6)×106S-1,ΓP6D=(4.1±0.3)×106S-1,and collisional transfer cross sections σ8S=(7.9±0.7)×1013cm2,σ6D=(6.2±0.3)×10-13cm2.
Energy pooling (EP) was observed in Rb vapor following pulsed optical excitation to the 5P1/2 state. The 5P3/2 state was populated by the energy transfer process: Rb(5P1/2)+Rb(5S1/2) --> Rb(5P3/2)+Rb(5Sl/2). The resulting densities of Rb atoms at the 5P1/2 level were obtained from the absorption of narrow spectral line from a Rb hollow cathode lamp, connecting the 5P1/2 state to 7S state. Since the effective lifetimes of the 5P1/2 and 5P3/2 states are approximately equal, the densities of the 5P3/2 level were obtained from the D2 to D1 fluorescence ratios where D1 and D2 are lines of the 5P1/2 --> 5S1/2 and 5P3/2 --> 5S1/2 transition. Because the time of the fine structure exchanging is much shorter than the lifetime of the 5D state, the fluorescence originating from the 5D state produced by the 5P1/2 + 5P3/2 and 5P3/2 + 5P3/2 processes follows the instantaneous production rate of the 5P1/2 + 5P1/2 process. It is clear that 5P/2 + 5P3/2 and 5P3/2 + 5P3/2 collisions can significantly influence the results obtained for the 5P1/2 + 5P1/2 rate since the energy defect for 5D state is much smaller for 5P1/2 + 5P3/2 and 5P3/2 + 5P3/2 collisions than for 5P1/2 + 5P1/2 collisions. Effective lifetimes of the 5P levels were calculated using radiation trapping theory. The time-integrated populations and signals were studied and analyzed. The resulting fluorescence included the direct component emitted in the decay of the optically excited 5P1/2 state and the sensitized component arising from the collisions for populating 5D state at different cell temperature. These relative intensities were combined with the measured excited atom densities to yield absolute energy-pooling rate coefficients. The cross sections (in units of 10(-14) cm2) for the energy-pooling collisions [i. e. , 5P1/2 + 5P1/2, 5P1/2 + 5P3/2, 5P3/2 + 5P3/2] are 0.78, 2.9 and 3.1, respectively. The dependence of the rates upon energy defect deltaE was examined, but the 5D3/2 level was approximately equally populated in 5P3/2 + 5P3/2 (deltaE = 68 cm(-1)) and 5P3/2 + 5P1/2 (deltaE = 306 cm(-1)) collisions. The 5P1/2 + 5P3/2 collisions are as efficient as 5P3/2 + 5P3/2 for populating 5D3/2 state.
Applying the CW laser absorption and fluorescence method,the cross sections for the fine structure mixing and quenching of the Rb(5P)state,induced by collision with N2 molecules,have been measured.Cesium atoms were optically excited to the 5P3/2 state.The excited atom density and spatial distribution were mapped by monitoring the absorption of a counterpropagating single mode laser beam,turned to the 5PJ→7S1/2 transitions.The effective radiative rates were calculated for the 5PJ→5S transitions.The fluorescence intensity I794 of the sensitized 5P1/2→5S1/2 emission was measured as a function of N2 density in the range 0.5×1016N4×1016cm-3 at constant temperature T=340 K.It was found that the quantity N/I794 exhibited a parabolic dependence on N,confirming that the quenching of the 5PJ states is due to collision with N2 molecules,not Rb ground state atoms.The coefficients of the second-order polynomial fitted through the measured data yielded the cross sections σ3/2→1/2=(10.43±3.54)×10-16cm2 and σD=(9.8±3.4)×10-16cm2 for the 5PJ fine-structure mixing and quenching,respectively,due to collision with N2 atoms.Our values for these cross sections are in agreement,within combined error bars,with values we have recently obtained under different experimental conditions.
The Rb(5D,7S)+H2→RbH+H photochemical reaction has been studied.The RbH molecules are formed in three-body reactive collisions between exited 5D or 7S atoms and ground state H2 molecules.Using two-photon absorption.Rb vapor mixed with Hz gas was irradiated in a glass fluorescence cell with pulses of 778.2nm or 760.1nm radiation from a YAG laser pumped OPO laser,populating one of the 5D and 7S states by two-photon absorption.The resulting fluorescence included a direct component emitted in the decay of the optically excited state and a sensitized component arising from the collisionally populated.The measured fluorescent intensities are proportional to the products of the appropriate population.The rate equations were solved.We estimated the value of cross sections for collisional energy transfer from Rb(5D) to Rb(7S), from Rb(7S)to Rb(5D) to be (6.9±1.4)×10-17 and(2.1±0.4)×10-16 cm2,respectively.The cross sections for reactive collisions Rb(5D)+H2RbH+H and Rb(7S)+H2→RbH+H are (4.3±1.1)×10-17 and(5.8±1.5)×10-17 cm2,respectively.The relative reactivity with H2 for two studied atoms is in an order of Rb(7S)Rb(5D).
Rb vapor, mixed with H2 or He, was irradiated in a glass fluorescence cell with pulses of radiation from a YAG-laser-pumped OPO laser, populating 5D or 7S state by two-photon absorption. The temperature dependence of the cross sections for 5D-7S transfer induced by collisions with He atoms and H2 molecules was determined using methods of atomic fluorescence. The resulting fluorescence included a direct component emitted in the decay of the optically excited state and a sensitized component arising from the collisionally populated state. At the different densities, the authors have measured the relative time-integrated intensities of the components and fitted a three-state rate equation model to obtain the reactive and nonreactive cross sections for Rb(7S-5D)-H2, He collisions. The cross sections of transfer for Rb(7S)+H2-->Rb(5D)+H2 decrease with increasing T. The cross sections for 5D-->7S increase with increasing T. At the different temperatures, the cross sections of transfer for (7S-5D)-He collisions coincide with the principle of detailed balance. The total transfer rate coefficients out of the 7S or 5D state for He were small. The total quenching rate coefficient out of the 7S or 5D state was much larger for H2. In the case of H2, the quenching rate coefficient corresponds to reaction and nonreactive energy transfer. In reaction of Rb(7S, 5D)+H2-->RbH+H, the ratio between the reactive cross sections was found to be sigma(-)[Rb(7S)+H2]/sigma(-)(Rb(5D)+H2]=1.5. The relative reactivity with H2 was in an order of Rb(7S)>Rb(5D).