Int. J. Mol. Sci. 2012, 13(2), 2501-2514; doi:10.3390/ijms13022501

Article
Spectroscopic Parameter and Molecular Constant Investigations on Low-Lying States of BeF Radical
Zun Lue Zhu *, Qing Peng Song , Su Hua Kou , Jian Hua Lang and Jin Feng Sun
College of Physics & Information Engineering, Henan Normal University, Xinxiang 453007, China; E-Mails: shangen1987@163.com (Q.P.S.); coco13141@126.com (S.H.K.); langjianhua87@163.com (J.H.L.); jfsun@htu.cn (J.F.S.)
*
Author to whom correspondence should be addressed; E-Mail: zl-zhu@htu.cn; Tel.: +86-373-332-6375; Fax: +86-373-332-6375.
Received: 12 December 2011; in revised form: 3 February 2012 / Accepted: 9 February 2012 /
Published: 22 February 2012

Abstract

: The potential energy curves (PECs) of X2+, A2Πr and B2+ states of BeF radical have been investigated using the complete active space self-consistent-field (CASSCF) method, followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach at the correlation-consistent basis sets, cc-pV5Z for Be and aug-cc-pV6Z for F. Based on the PECs of X2+, A2Πr and B2+ states, the spectroscopic parameters (De, Re, ωe, ωeχe, αe and Be) have also been determined in the present work. With the PECs determined at the present level of theory, vibrational states have been predicted for each state when the rotational quantum number J equals zero (J = 0). The vibrational levels, inertial rotation and centrifugal distortion constants are determined for the three states, and the classical turning points are also calculated for the X2+ state. Compared with the available experiments and other theories, it can be seen that the present spectroscopic parameter and molecular constant results are more fully in agreement with the experimental findings.
Keywords:
potential energy curve; dissociation energy; spectroscopic constant; molecular constant

1. Introduction

Fluorides are a very important chemical species with broad applications in chemistry. The chemical property of fluorine is very lively and highly oxidized. In combination with other elements, resultant properties will be heat-resistant and difficult to erode by drugs and solvents. Fluorine is widely used in domestic appliances, office automation equipment, semiconductors, automobiles and other fields. Recently, with the development of calculation technology of quantum chemistry, more and more interest has been concentrated on the beryllium compounds [16]. As a simple fluoride compound, Beryllium Monofluoride (BeF) has been widely studied, both experimentally [711] and theoretically [1221].

However, as can be seen in the literature, the experimental dissociation energies D0 of BeF greatly differ from each other. For example, the value reported by Hildenbrand and Murad [7] in 1966 is of 5.85 eV and the value determined by Farber and Srivastava [9] in 1974 is of 6.26 eV. Whereas this value collected in Reference [10] by Herzberg in 1950 is of 5.4 eV and collected in Reference [11] by Huber and Herzberg in 1979 is of 6.26 or 5.85 eV. Obviously, it needs to be clarified urgently.

In theory, the spectroscopic parameters including the dissociation energy De have been widely studied in the past several decades [1221]. On the one hand, the De values still show a wide variation. For example, Roach and Kuntz [12] investigated the De in 1982, and gave a value of 3.94 eV. Partridge et al. [13] calculated the De in 1984 with a value of 5.94 eV. On the other hand, it is still in question whether the potential barrier on the ground-state potential energy curve exists or not. For example, Roach [12] and Machado et al. [17] thought that the barrier obtained here, and the spectroscopic parameters are accurately determined. Finally, it is considered that numerically solving the radial Schrödinger equation is possible, but Marian [14] and Ornellas et al. [18] did not think so. Furthermore, some theoretical information [14,18,20,21] is available about the excited states of BeF. Some vibrational manifolds (such as vibrational levels, initial rotation and centrifugal distortion constants) have been reported in the literature, which have important applications in the vibrational transition calculations. All these aspects motivated us to perform the present investigations.

One of the purposes of this investigation is to determine the accurate potential energy curves of X2+, A2Πr and B2+ states for BeF radical, using the full valence complete active space self-consistent field method [22,23], followed by the highly accurate valence internally contracted multireference configuration interaction approach [24,25] in combination with the correlation-consistent basis sets [2628], cc-pV5Z for Be and aug-cc-pV6Z for F atom. The spectroscopic parameters and vibrational manifolds are determined for these three states, using the obtained PECs of BeF radical, with the help of VIBROT module in MOLCAS 7.4 program package [29].

2. Theoretical Approach

We calculate the PECs of X2+, A2Πr and B2+ states of BeF by the CASSCF approach, followed by the MRCI calculations. Therefore, the full valence CASSCF is employed as the reference wavefunction for the MRCI calculations in the present work. For the PEC calculations, the MRCI theory has proven particularly successful [3035]. The present calculations are carried out in MOLPRO 2008.1 program package [36] with the largest correlation-consistent basis set, cc-pV5Z for Be and aug-cc-pV6Z for F atom.

BeF is of Cv point group symmetry. According to the molecular theory and the requirement of MOLPRO program package, it must be replaced by C2v symmetry with the order of the irreducible representations as a1/b1/b2/a2 in the calculations. In detail, eight molecular orbitals (MOs) are put into the active space, including four a1, two b1 and two b2 symmetry MOs, which correspond to the 2s shell of Be and 2s2p shell of F atom. The rest of the electrons in the BeF radical are put into the closed-shell orbitals, including two a1 symmetry MOs. When we use these MOs (six a1, two b1, two b2) to calculate the PECs of the BeF radical, we find that the obtained PECs are smooth for all these basis sets over the present internuclear distance range.

In general, the PECs calculations are made at intervals of 0.02 nm over the internuclear distance range from 0.0522 to 2.0472 nm. Near the equilibrium position, we chose the interval to be of 0.005 nm so that the properties of the PECs are displayed more clearly. With the PECs determined at the different basis sets, the spectroscopic parameters (De, ωe, ωeχe, αe, Be and D0) are evaluated. By comparison with the experiments [711], we find that the best favorable spectroscopic parameter results can be obtained at the basis sets, cc-pV5Z for Be and aug-cc-pV6Z for F atom.

In order to take into consideration the relativistic effects on the spectroscopic parameters, the Douglas-Kroll one-electron integrals are used with the basis sets cc-pV5Z for Be and aug-cc-pV6Z for F. We notice that almost no accuracy improvements can be made for the spectroscopic parameters after considering the relativistic corrections. Therefore, vibrational manifold calculations are made at the PECs obtained at the non-relativistic condition.

3. Results and Discussion

3.1. PECs of the BeF and Spectroscopic Parameters

The PECs of BeF radical are shown in Figure 1. As shown in the figure, the A2Πr curve and the B2+ curve are all marginally repulsive at long range, but they do not converge. The A2Πr state and the X2+ state have the same dissociation channel Be(1Sg) +F(2Pu), which is different from Be(3Pu) +F(2Pu) for the B2+ state. During the course of the PEC investigation of the X2+ state, the existence of the barrier was a hot topic and should be stressed here, however, that it is not the main goal of the present work. To illustrate the existence of the barrier of the PEC of the X2+ state, a magnified image for the PEC of the X2+ state has been shown in Figure 2. It has been found in our calculations that there is a small barrier in the curve of X2+ state which has been found at the internuclear separation, 0.3372 nm, and the barrier height is of 0.18 eV. A similar situation was also found by Roach [12] and Machado [17], but not by Marian [14] and Ornellas et al. [18]. Ornellas et al. [18] did not observe the small hump since the interval used was too large when they calculated the PEC. Marian [14] paid attention to calculating the spin-orbit coupling, and he considered 42 reference state functions to generate the CI wavefunction. In similarity with Reference [18], the interval was also too large in his calculations [14]. A wide barrier of 0.79 eV has been found in the PEC of the A2Πr state, similar to the value reported by Marian [14] and Ornellas et al. [18], 0.81 eV and 0.79 eV, respectively. A similar feature has also been found for the B2+ curve of the BeF radical. Near 0.18nm, the B2+ state unfolds a sharp avoided crossing with the repulsive covalent state correlating with the dissociation channel Be(3Pu) +F(2Pu). So the avoided crossing and the ionic character are responsible for the unusual shape of these potential curves.

With the PECs determined, the spectroscopic parameters and molecular constants are evaluated with the VIBROT module in MOLCAS 7.4 program package. In order to conveniently compare the present results, we compiled the spectroscopic parameters together with the available experiments [711] and other theories [1221] in Table 1 for the BeF radical.

A number of theoretical investigations had been made on the spectroscopic parameters of the X2+ state of the BeF radical. Partridge et al. [13] in 1984 carried out the Re, De and D0 calculations using Hartree-Fock (HF) method and some empirical formulas with Slater-type orbital (STO) basis set. Although their calculational results are close to the experiments, the existing experimental values and some empirical formulas were used and only two spectroscopic parameters were evaluated in their investigations. In 1985, Marian [14] investigated the PEC using multireference doubles configuration interaction approach (MRDCI) method with the GTO DZP AO basis set. With the aid of PEC, they calculated several spectroscopic parameters. We can find that his ωeχe is slightly smaller than the present one when compared with the corresponding experiments, though his Re is in more agreement with the experiments than ours. Langhoff et al. [15] in 1986 calculated Re and ωe by two methods. We find that their most favorable results were obtained by the configuration interaction (CI) approach. As shown in Table 1, it is believed that these results are the most accurate values so far, but only limited spectroscopic parameters are derived. Langhoff et al. [16] later evaluated the Re and ωe by three approaches. By comparison with the experiments, we find that their most favorable results were obtained with the singles and doubles configuration interaction (SDCI) approach. Also, the values are in more agreement with the experiments when compared with the present ones. However, their investigations were not concerned with other spectroscopic parameters.

Later, Machado and Ornellas [17] in 1989 made the PEC calculations by multireference singles and doubles configuration interaction approach (MRSDCI) with the Gaussian sets (5s, 3p) for Be and (7s, 4p) for F. As can be seen in Table 1, their ωe and ωeχe are too large when compared with the experiments. Three years later, Ornellas et al. [18] in 1992 made the PEC calculation for ground state. In the calculations, their approach is the MRSDCI and the basis sets are (14s10p3d1f)/[8s6p3d1f] for F and (11s6p1d)/[6s4p1d] for Be. By comparison with the present ones, it is not difficult to find that their ωeχe and ωe are slightly larger than the present experiments. Recently, Li and Hamilton [19] in 2001 calculated the Re using density functional theory (DFT) and MØller-Plesset (MP2) methods with three basis sets. Their most favorable results were obtained by DFT (BH and HLYP) approach with 6 − 311 + G* basis sets. However, they did not compute spectroscopic parameters apart from the Re and ωe. Recently, Pelegrini et al. [20] in 2005 performed some spectroscopic parameter calculations by the MRCI method with the aug-cc-pVQZ basis set. As tabulated in Table 1, their ωeχe is far from the measurements when compared with the present work. Furthermore, other important spectroscopic parameters (such as Be and αe) were not evaluated in their investigations.

For the A2Πr state, Walker and Richards [21] performed the Re and ωe calculations using two methods in 1967. We find that their optimal results were obtained by the configuration interaction (CI) approach. As shown in Table 1, their ωe is slightly smaller than the experiment data and other important spectroscopic parameters were not evaluated in their investigations. In 1985, Marian [14] investigated the PEC using MRDCI method with a GTO DZP AO basis set, with the aid of PEC, they calculated several spectroscopic parameters. We can find that his ωeχe is too large and his De is too small when compared with the experiments. Furthermore, αe was not evaluated in his investigations. Ornellas et al. [18] in 1992 made the PEC calculation for lowest-lying state. In the calculations, their approach is the MRSDCI and the basis sets are (14s10p3d1f)/[8s6p3d1f] for F and (11s6p1d)/[6s4p1d] for Be. By comparison, it is not difficult to find that their ωeχe and ωe are slightly larger than the present experiments when compared with the present ones. Pelegrini et al. [20] also performed some spectroscopic parameter calculations for the A2Πr state of the BeF radical using the MRCI method with the aug-cc-pVQZ basis set. As tabulated in Table 1, their ωeχe and ωe are far from the available measurements when compared with our work.

For the B2+ of BeF radical, few theoretical investigations have been made on the spectroscopic parameters. The earlier theoretical calculations were performed by Marian [14]. He investigated the PEC of BeF(B2+) using MRDCI method with a GTO DZP AO basis set. We can find that his ωe and ωeχe are too large when compared with the experiments. Furthermore, De and αe were not evaluated in his investigations.

According to the above analysis and discussion, on the whole, the spectroscopic parameters obtained in the present work have improved when compared with previous theoretical results. For example, for the X2+ state, the spectroscopic parameters, ωeχe, αe, ωe, Be and Re, deviate from the experiments [11] only by 0.11%, 0.57%, 0.90%, 1.60% and 0.81%, respectively. For the BeF(A2Πr), the spectroscopic parameters, ωeχe, αe, ωe, Be and Re, deviate from the experiments [11] only by 0.00%, 2.86%, 1.69%, 0.51% and 0.25%, respectively.

As for the dissociation energy De of BeF(X2+), it shows a wide variation. Roach and Kuntz [12] in 1982 made valence-bond (VB) calculations on the BeF(X2+) radical, and they obtained the value to be 3.94 eV. But they claimed that their VB calculations are not accurate enough to deduce the accurate value of De in Reference [12]. Partridge et al. [13] calculated the D0 with empirical formula and obtained the direct value of D0 to be 5.86 eV, and also gave the estimate result of 5.91 eV. The precision of the method is slightly lower than this work. Marian [14] investigated the PEC using MRDCI method with a GTO DZP AO basis set. They obtained De of 5.5 eV, however, he thought that the value is a little small. Langhoff et al. [15] calculated the De by the SCF method. As we know, the method is too simple so that the De result they obtained is not very credible. Machado and Ornellas [17] calculated the De by MRSDCI approach with the Gaussian sets (5s,3p) for Be and (7s,4p) for F. Ornellas et al. [18] computed the De by the MRSDCI method and the basis sets are (11s6p1d)/[6s4p1d] for Be and (14s10p3d1f)/[8s6p3d1f] for F. The basis sets they used are very small. Therefore, their values are less accurate. In the present work, the PEC of BeF(X2+) is computed using the highly accurate MRCI approach with the large basis sets, cc-pV5Z for Be and aug-cc-pV6Z for F. With the aid of PEC, the De is determined to be 6.22 eV, which should be relatively close to the true value.

In this paper, we also calculate the ΔTe of the A2Πr state is of 32,343.9 cm−1, while the value obtained by Marian [14], Ornellas et al. [18] and Pelegrini et al. [20] to be 34,814 cm−1, 33,974 cm−1 and 34,902 cm−1, respectively. And the ΔTe of the B2+ state is also calculated, and the value is of 48,877 cm−1, the data reported by Marian [14] to be 50,844 cm−1.

It is widely recognized that the accuracy of the spectroscopic parameters calculations mainly depends on the scanned results for the PEC of the electronic state by using CASSCF AND MRCI approach. The scanned results of the electronic state are related to the choice of the active space for a CASSCF and of the basis sets. For BeF radical, the each electronic state possesses different bonding orbitals at various internuclear sparations [14]. In order to obtain more accurate calculational results of PECS of BeF radical, eight molecular orbitals, including four a1, two b1 and two b2 symmetry MOs, are put into the active space, and the rest of the electrons in the BeF radical are put into two a1 symmetry closed-shell orbitals, which differ from Reference [20]. In addition, the appropriate choices of the basis sets and the calculational interval in the CASSCF calculation also conduce to the accurate calculational results. So we have reasons to believe that the present results are reliable.

3.2. Vibrational Manifolds

Based on the reliable PECs of the X2+, A2Πr and B2+ states, we determine their vibrational levels, inertial rotation and centrifugal constants when J = 0. And we also compute classical turning points for the ground state. Owing to the length limitation of the paper, we only tabulate some of these results for the vibrational states in Tables 27. To the best of our knowledge, no experimental data of molecular constants have been found in the literature, except several groups of theoretical results. But according to the remarkable agreement between the present spectroscopic parameters and the available experiments and the excellent accordance between the theoretical and the corresponding RKR data, we have reasons to believe that the results collected in Tables 27 are accurate.

As can be seen from Table 2, the present results are in excellent agreement with the theoretical data reported in the literature. For example, the deviations from the theories [17] are of only 0.25%, 0.12%, 0.02% and 0.23% when υ = 1, 3, 5 and 7, respectively, and the deviations from the theories [18] deviate only by 0.23%, 0.33%, 0.45% and 0.64%, respectively. Therefore, we can say that the present calculations are accurate. Furthermore we can conclude that the values of vibrational levels and classical turning points presented in Table 3 must be reliable.

Similar to the vibrational level spacings, there are two groups of theoretical data [17,18] concerned with the inertial rotation constant Bυ and centrifugal distortion constant Dυ of BeF(X2+). For a convenient comparison with the present results, we also tabulate them in Table 4. By simple calculations, it is not difficult to find that excellent agreement exists between the present results and the theoretical data. For example for the Bυ, the deviations from the theory [17] are only 0.14%, 0.47%, and 0.51% when υ =0, 2 and 4, respectively. As to the centrifugal distortion constant Dυ, good accord also exists between the present results and the available theoretical data [17,18]. Therefore, the present calculations are accurate. According to these, the calculations of the centrifugal distortion constants presented in Table 5 should be reliable.

As can be seen from Table 6, the present results are in excellent agreement with the experiments [14]. For example, the deviations from the experiments [14] are only 0.13%, 0.19%, 0.27% and 0.38% when υ = 0, 2, 4 and 6, respectively. Therefore, we can say that the present calculations are accurate. For the inertial rotation constant Bυ, the deviations of the present values from the experiments [8] are of 0.50% and 0.45%, when υ = 0 and 1, respectively.

To the best of our knowledge, no experimental and theoretical data of vibrational levels and molecular constants for BeF(B2+) has been found in the literature. However, according to the remarkable agreement between the present spectroscopic parameters and the available experiments [8,11], we have reasons to believe that the results collected in Tables 5 are accurate.

4. Conclusions

In the present work, the PECs of X2+, A2Πr and B2+ states of BeF radical have been investigated by the MRCI approach with large correlation-consistent basis sets, cc-pV5Z for Be and aug-cc-pV6Z for F. Based on the PECs of these three states, the spectroscopic parameters and molecular constants are determined in the present work, and the values are in excellent agreement with the experimental data. With the PECs of these states determined at the MRCI level of theory, the vibrational levels, inertial rotation and centrifugal distortion constants are predicted, and the classical turning points are also calculated for the X2+ state when J = 0. On the whole, comparison with the available experiments and theories shows that the present calculations are both reliable and accurate.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 10874064), the Natural Science Foundation of Henan Province in China (Grant No. 2008A140008), and the Key Teachers Foundation of Henan Province in China (Grant No. 2008043).

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Ijms 13 02501f1 200
Figure 1. Potential energy curves (PECs) of the BeF.

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Figure 1. Potential energy curves (PECs) of the BeF.
Ijms 13 02501f1 1024
Ijms 13 02501f2 200
Figure 2. PEC of the X2+state.

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Figure 2. PEC of the X2+state.
Ijms 13 02501f2 1024
Table 1. Spectroscopic parameter comparison with available measurements and other theories for BeF radical.

Click here to display table

Table 1. Spectroscopic parameter comparison with available measurements and other theories for BeF radical.
SourceDe/eVRe/nmωe/cm−1ωeχe/cm−1Be/cm−1αe/cm−1D0/eV
X2+
This work6.220.13721236.129.111.46510.01756.14
Exp [7]------------------------5.85
Exp [9]------------------------6.26
Exp [10]5.480.136141265.69.121.48770.016855.4
Exp [11]6.34 or 5.930.13611247.369.121.48890.01766.26 or 5.85
Theory [12]3.94------------------------
Theory [13]5.940.135----------------5.86
Theory [14]5.50.136912588.81.472--------
Theory [15]
SCF----0.13521280------------5.88
CI(SD)----0.13631250------------5.94
Theory [16]----0.136371250----------------
Theory [17]6.000.137111265.79.261.4690.01695.92
Theory [18]5.820.13691272.59.521.4720.01695----
Theory [19]----0.1371240----------------
Theory [20]----0.135311339.38.34------------
A2ΠrTe/cm−1
This work2.320.13971174.28.781.4130.017032,343.9
Exp [8]----0.139351171.2-----1.420240.017533,187
Exp [10]----0.139411172.68.781.41860.016133,233.6
Exp [11]1.81 or 2.220.139351154.678.781.420240.017533,233.6
Theory [14]1.170.1387118313.51.433----34,814
Theory [18]1.690.13951175.48.81.4120.0171333,974
Theory [20]----0.13851226.87.42--------34,902
Theory [21]----0.14371116----------------
B2+
This work2.600.13321351.112.71.5540.014948,877
Exp [8]----0.13351350.8----1.547----49,573
Exp [11]2.51 or 2.9770.13351350.812.61.547----49,570
Theory [14]----0.1321150313.11.580----50,844
Table 2. Comparison of the present and other theoretical vibrational level spacings (in cm1), G(υ + 1) − G(υ).

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Table 2. Comparison of the present and other theoretical vibrational level spacings (in cm1), G(υ + 1) − G(υ).
υThis workRef. [17]Ref. [8]Ref. [18]υThis workRef. [17]Ref. [8]Ref. [18]
01254.01255.61254.51247.2141021.11024.41009.31003.7
11236.41239.51233.61229.0151005.41007.7993.0987.4
21218.91221.61215.41210.816989.8991.5997.0
31201.51202.91197.51192.817947.3975.7961.4
41184.51184.81179.71175.018958.8960.4
51167.51167.71162.31157.419943.5945.6
61150.71151.91144.51139.520928.2931.3
71134.01136.61126.81122.221912.9917.5
81117.51121.41109.41104.922897.8904.0
91101.21106.21092.11086.823882.6890.8
101084.91090.61075.11070.624867.5877.8
111068.81074.61058.51053.725852.5865.1
121052.81058.21042.01036.926837.5
131036.91041.31025.61020.227822.5
G(0)634.1634.4635.0----
Table 3. Vibrational levels and classical turning points for BeF(X2+) radical when J = 0 at the MRCI level of theory.

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Table 3. Vibrational levels and classical turning points for BeF(X2+) radical when J = 0 at the MRCI level of theory.
υG(υ)/cm−1Rmin/nmRmax/nmυG(υ)/cm−1Rmin/nmRmax/nm
0634.0750.131020.144233836,940.2700.102740.25274
11888.0920.126960.149983937,598.0680.102530.25580
23124.4500.124380.154274038,240.7670.102320.25890
34343.3330.122400.157984138,868.3120.102120.26207
45544.9190.120770.161354239,480.6740.101930.26530
56729.3780.119370.164504340,077.7680.101750.26861
67896.8760.118150.167514440,659.5360.101570.27199
79047.5680.117050.170394541,225.9030.101390.27545
810,181.6050.116060.173194641,776.7890.101230.27899
911,299.1290.115160.175924742,312.1040.101070.28265
1012,400.2790.114320.178604842,831.7500.100920.28639
1113,485.1830.113550.181234943,335.6220.100770.29026
1214,553.9650.112830.183835043,823.6040.100630.29425
1315,606.7420.112160.186415144,295.5720.100490.29837
1416,643.6230.111530.188965244,751.3900.100370.30263
1517,664.7130.110940.191505345,190.9110.100240.30706
1618,670.1090.110370.194005445,613.9780.100200.31166
1719,659.9020.109840.196555546,020.4170.100100.31646
1820,634.1770.109340.199075646,410.0440.099900.32147
1921,593.0130.108860.201585746,782.6550.099800.32673
2022536.4840.108390.204115847138.0330.099710.33226
2123464.6570.107960.206635947475.9380.099610.33809
2224377.5910.107540.209166047796.1090.099530.34428
2325275.3450.107150.211716148098.2630.099450.35088
2426157.9650.106770.214266248382.0860.099370.35794
2527025.4980.106390.216836348647.2320.099300.36555
2627877.9800.106050.219436448893.3200.099240.37383
2728715.4460.105710.222046549119.9230.099180.38289
2829537.9220.105390.224676649326.5590.099120.39295
2930345.4290.105080.227326749512.6850.099070.40426
3031137.9850.104780.230016849677.6740.099030.41721
3131915.5990.104490.232726949820.7970.098990.43242
3232678.2770.104210.235467049941.1830.098960.45089
3333426.0180.103940.238247150037.7650.098940.47456
3434158.8170.103680.241067250109.1760.098920.50785
3534876.6620.103440.243917350153.5190.098910.56546
3635579.5350.103190.246817450165.9990.098960.65321
3736267.4140.102970.24975
Table 4. Rotational constants for BeF(X2+) radical.

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Table 4. Rotational constants for BeF(X2+) radical.
υBυ/cm−1Dυ/cm−1

This workTheory[17]Theory[18]This workTheory[17]Theory[18]
01.4661.46401.4637.7557.8657.367
11.4401.44711.4447.7107.8887.630
21.4231.42971.4277.6677.8277.647
31.4071.41321.4117.6237.8207.419
41.3901.39711.3947.5817.8177.366
51.3751.38081.3777.5407.7286.406
61.3591.36411.3617.4987.6697.506
71.3431.34751.3457.4597.6956.988
81.3271.33101.3297.4207.6307.366
91.3111.31461.3137.3837.6057.688
101.2961.29841.2977.3467.5556.406
111.2807.310
121.2657.277
131.2507.245
141.2347.214
151.2197.184
161.2047.157
171.1897.130
181.1747.107
191.1597.084
201.1457.064
Table 5. The centrifugal distortion constants for the BeF(X2+) radical when J = 0.

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Table 5. The centrifugal distortion constants for the BeF(X2+) radical when J = 0.
υHυ (×1011)/cm−1Lυ (×1017)/cm−1Mυ (×1022)/cm−1Nυ (×1027)/cm−1Oυ (×1032)/cm−1
01.4027100−4.86716111.9911130−2.8402586−2.0392494
11.4053343−5.11752721.6143796−3.1990403−2.2434658
21.4053989−5.39178041.2293437−3.5529674−2.4676094
31.4028724−5.68896720.83591753−3.9116409−2.7280207
41.3977284−6.00835440.43329623−4.2808699−3.0356308
51.3899449−6.34937670.020141443−4.6670931−3.4018218
61.3795027−6.7116605−0.40542105−5.0774004−3.8395702
71.3663844−7.0950461−0.84581042−5.5195056−4.3611048
81.3505725−7.4996087−1.3039962−6.0018194−4.9798226
91.3320486−7.9256784−1.7835120−6.5335708−5.7128176
101.3107919−8.3738600−2.2884790−7.1248038−6.5756507
111.2867778−8.8450532−2.8236361−7.7866333−7.5878382
121.2599765−9.3404730−3.3943722−8.5313740−8.7747008
131.2303516−9.8616728−4.0067932−9.3727447−10.161238
141.1978589−10.410568−4.6677733−10.326299−11.793475
151.1624448−10.989467−5.3850704−11.409132−13.677149
161.1240448−11.601095−6.1673928−12.641287−15.864538
171.0825822−12.248641−7.0245304−14.045587−18.441352
181.0379661−12.935792−7.9675652−15.648035−21.437787
190.99008998−13.666785−9.0089937−17.479025−24.938023
200.93882954−14.446467−10.162999−19.573574−29.013928
Table 6. Comparisons of vibrational levels and molecular constants with experiments and theories calculated for BeF(A2Πr) radical when J = 0.

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Table 6. Comparisons of vibrational levels and molecular constants with experiments and theories calculated for BeF(A2Πr) radical when J = 0.
υG(υ)/cm−1Bυ/cm−1Dυ (×106)/cm−1

This workRef. [14]Exp. *This workRef. [18]Exp. [8]This workRef. [18]Exp. [8]
0584.86588584.11.40451.40411.41158.1598.1528.40
11741.8417441739.11.38761.38661.39398.0958.1048.26
22882.1628722876.61.37091.36968.0497.953
34005.6939733996.51.35451.35287.9818.015
45112.9250475098.91.33801.3367.9267.995
56203.8660976183.71.32711.31927.8737.953
67278.6271247250.91.30561.30267.8327.884
78337.2781308300.61.28971.28617.7777.852
89380.0791179332.71.27391.26957.7037.855
910407.471008810347.31.25841.25287.6357.856
1011419.761104411344.31.24301.23617.6037.831
1112416.791292513285.61.22767.611
1213398.111385514229.91.12127.634
1314363.211477915156.71.19617.603
1415312.161.18077.451
1516246.141.1667.162
1617167.191.15266.895
1718076.981.13976.919
1818974.861.12577.418
1919275.902.33276.9808
2019313.932.07312.9969

*Taken from the reference in Reference [14].

Table 7. Vibrational levels and molecular constants for the B2+ state of BeF radical.

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Table 7. Vibrational levels and molecular constants for the B2+ state of BeF radical.
υG(υ)/cm−1Bυ/cm−1Dυ(×106)/cm−1
0672.361.54518.263
11997.791.52488.310
23297.211.50428.533
33565.790.36691.304
43953.600.37151.377
54342.890.37571.428
64570.021.48338.444
74733.410.37951.483
85124.940.38321.533
95517.250.38661.584
105815.891.46218.580
115910.180.38981.632
126303.560.39281.686
136697.250.39571.741
147033.161.43998.771
157091.100.39841.791
167484.950.40101.849
177878.670.40341.909
188220.251.41768.725
198272.160.40572.001
208665.010.40792.056
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