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The Complete Active Space Self Consistent Field (CASSCF) with Multi Reference Configuration Interaction (single and double excitation with Davidson correction) MRCI + Q method has been used to investigate the potential energy curves of the 17 low-lying triplet electronic states of the molecule BP. The harmonic vibrational frequency ω
_{e}, the inter-nuclear distance at equilibrium Re, the rotational constant
B_{e}, the electronic energy with respect to the minimum ground state energy
T_{e}, and the permanent dipole moment have been also calculated. A literature review shows a strong correlation between our investigated data and those previously published either theoretically or experimentally. This work introduces, for the first time, a study of 14 new electronic states. Our spectroscopic data can be a conducive to further work on BP molecule in both experimental and theoretical research.

Although the molecular III-V family have many unique chemical and physical properties, boron phosphate has a good translucent, good adhesion, smaller index of ionicity and low internal stress level. It also, constitutes an excellent example of an almost perfect covalence heteronuclear diatomic molecule. This low-heteropolarity gives striking features to the BP system. Many experimental studies were done on diatomic molecules by considering either one electronegative and one electropositive atom or two electronegative atoms. From the other side, no extensive studies were done on diatomic molecules of two atoms belonging to electropositive groups [

In literature, BP molecule was originally studied by Gingerich et al. [^{3}P state is the ground state, while the first excited state ^{1}S^{+} lies 0.3 eV above the ground state. Since the BP molecule has very close electronic states of different multiplicity, there are difficulties for determining its molecular parameters in the fundamental and excited states. Using Bader’s theory of atoms in molecules [^{1}S^{+}, ^{3}S^{−}, and ^{3}P and concluded that ^{3}P is the fundamental state in agreement with the results of Boldyrev and Simons [

The focus of this study is devoted to an accurate description of the ground and electronically excited triplet electronic states. In order to emphasize the accuracy of our work, we used the multi-reference configuration interaction (MRCI+Q) model expansion. The spectroscopic constants R_{e}, T_{e}, B_{e}, ω_{e}, …for each of the corresponding electronic states have been investigated along with the static dipole moment.

The correlation energy for a certain state is the difference between the exact eigenvalue of the Hamiltonian and its expectation value in the HF approximation. The configuration interaction (CI) treatment of this electron correlation is obtained by adding to the HF wavefunction terms that represent promotion of electrons from occupied to virtual (unoccupied) orbital that are singly, doubly, and triply excited. Each Slater determinant D, or linear combination of a few determinants, represent an idealized configuration, called configuration state function (CSF). The CI wavefunctions then, are linear combinations of CSFs. The most widely-used implementations of CI are multiconfigurational self consistent field (MCSCF) method. In this method, one writes the molecular wavefunction as a linear combination of CSFs and varies not only the expansion coefficients but also the forms of the molecular orbitals in the CSFs. CASSCF wavefunctions are often used as the starting point for MRCI calculation. When a CASSCF wavefunction is used for a MRCISD calculation, the number of CSFs may be too many to deal with, so one procedure used to reduce the amount of computations is the internally contracted MRCI. The theoretical study of the low-lying singlet and triplet electronic states of the molecule BP have been studied by using the state averaged Complete Active Space Self-Consistent Field (CASSCF) procedure [_{0}, 4s, 3d_{0}, 4p_{0}) and 4p (B:2p_{±}_{1}; P:3p_{±}_{1}, 3d_{±}_{1}, 4p_{±}_{1}) 1d (P:3d_{±2}) orbitals in the C_{2v} molecular orbitals are distributed into the irreducible representation a_{1}, b_{1}, b_{2} and 1a_{2} in the following way 6a_{1}, 4b_{1}, 4b_{2}, 1a_{2} noted [6, 4, 4, 1]. The 1s^{2} 2s^{2} of B and 1s^{2} 2s^{2} 2p^{6} 3s^{2} of P atoms were frozen in the MCSCF procedure. The number of active orbitals and valence electrons are 16 and 8 respectively.

Potential energy curves (PECs) of the 17 triplet electronic states, in the representation

One can notice the deep potential wells for the low doublet and shallower wells for the higher excited electronic states. Moreover, some crossings and avoided crossings of abscissas R_{c} and R_{ac} respectively have been obtained between the potential energy curves. If the two curves correspond to states of different symmetry cross where the crossing in this case is strictly allowed. But if these wavefunctions have the same symmetry, the two

states will only be diabatic solutions of the problem. They will mix with each other to give two adiabatic solutions which no longer cross and the crossing becomes avoided. The adiabatic solutions of the Schrödinger equation Y_{1} and Y_{2} are obtained by linear combinations of the diabatic ones where the variation method is used to solve for the coefficients. Such crossings or avoided crossings can dramatically alter the stability of molecules and the trend of the potential energy curve. From ^{3}D/(2)^{3}D at 2.23 Å and (2)^{3}D/(3)^{3}D at 2.77 Å. More over the wells are absent from some states which are unbound states. The electronic states (2)^{3}P presents double wells where we calculated the spectroscopic constants in ^{2s+1}Λ^{(±)}. These curves are drawn versus the internuclear distance 1.2 Å ≤ R ≤ 5.5 Å in _{e}, the harmonic vibrational frequencies ω_{e}, the relative energy separations T_{e}, and the rotational constants B_{e} for these electronic states have been calculated and given in

The comparison of our calculated internuclear distance R_{e} for the ground state X^{3}P with those given in literature, either experimental or theoretical, shows a very good agreement with relative difference of 0.4% (Ref. [_{e}/R_{e} ≤ 1.4% (Ref. [_{e},

States | T_{e} (cm^{−1}) | R_{e} (Å) | w_{e} (cm^{−1}) | B_{e} (cm^{−1}) |
---|---|---|---|---|

X^{3}P | 0.0^{a} | 1.740^{a } 1.7595^{b} 1.7478^{c1 } 1.7520^{c2} 1.7539^{d1 } 1.7538^{d2} 1.757^{e1} 1.764^{e2} 1.747^{e3} 1.758^{f } 1.747^{g} | 1026.08^{a } 941.39^{ c2} 934.69^{d1 } 934.800^{d2} 1148^{e1} 897^{e2} 941^{e3 } 1148^{f} 973^{g} | 0.6985^{a } 0.6762^{c2} 0.674706^{d1 } 0.674727^{d2} |

(1)^{3}Σ^{− } | 5783.98^{a} 6708.3^{b } 7612^{c1 } 6822^{c2 } 7469^{c3 } 7412^{c4 } 6987.19^{d1} 7062.91^{d2} | 1.933^{a } 1.9730^{b} 1.9616^{c1 } 1.9690^{c2} 1.9623^{d1 } 1.963^{d2 } 1.9424^{e1} 1.9684^{e3 } 1.943^{f} 1.694^{g} | 773.14^{a } 633.75^{c2 } 636.72^{d1 } 642.760^{d2} 585^{e1 } 634^{e3 } 585^{f} 925^{g} | 0.5622^{a } 0.5353^{c2} 0.53877^{d1 } 0.539617^{d2} |

(2)^{3}Π 1^{st} minimum | 25628.34^{a } | 1.903^{a } 1.7539^{d } 2.019^{g} | 892.2^{a } 934.748^{d } 522^{g} | 0.5808^{a } 0.674698^{d} |

(2)^{3}Π 2^{nd} minimum | 30737.85^{a} | 2.649^{a } | 302.9^{a} | 0.2999^{a} |

(3)^{3}Φ | 30740.99^{a} | 1.915^{a} | 798.56^{a} | 0.574^{a} |

(1)^{3}Σ^{+} | 33989.58^{a} | 1.945^{a } | 566.19^{a} | 0.556^{a} |

^{} | 36500^{a} | 4.081^{a} | 184.58^{a} | 0.1069^{a} |

(2)^{3}Σ^{−} | 35650^{a } | 3.303^{a} | 153.4^{a} | 0.1923^{a} |

(3)^{3}Σ^{−} | 36515^{a} | 5.502^{a} | 147.56^{a} | 0.651^{a} |

(2)^{3}Δ | 36530^{a} | 5.649^{a} | 175.611^{a} | 0.690^{a} |

(1)^{3}Δ | 39173.33^{a} | 1.968^{a} | 388.4^{a} | 0.5417^{a} |

(2)^{3}Δ | 42374.78^{a} | 2.574^{a} | 169.4^{a} | 0.3185^{a} |

(2)^{3}^{+} | 42568.19^{a} | 5.516 | 413.51 | 0.451 |

(3)^{3}Δ | 42561.9^{a} | 4.246^{a} | 321.6^{a} | 0.1158^{a} |

(2)^{3}Σ^{+} | 42371.80^{a} | 2.557^{a} | 201.36^{a} | 0.315^{a} |

(4)^{3}Σ^{−} | 53812.4^{a} | 1.914^{a} | 715.09^{a} | 0.546^{a} |

(5)^{3}Σ^{−} 1^{st} minimum | 55241.67^{a} | 1.879^{a} | 143.02^{a} | 0.595^{a} |

(5)^{3}Σ^{−} 2^{nd} minimum | 42569.96^{a} | 4.843^{a} | 573.69^{a} | 0.804^{a} |

^{a}Present theoretical study. ^{b}Ref [^{c}Ref [^{d}Ref [^{e}Ref [^{f}Ref [^{g}Ref [

for the first excited state (1)^{3}Σ^{−}, with those given in literature where the relative difference is 1.5% (Ref. [_{e}/R_{e} ≤ 2.1% (Ref. [_{e}/R_{e} = 7.7% for the state (2)^{3}Π.

One can notice the large discrepancy between the given values for the harmonic frequency ω_{e} in literature, but our calculated value is found to be between the highest and lowest values as 934.69 cm^{−1} < 1026.1 cm^{−1} < 1148 cm^{−1}. While our calculated value of w_{e} is greater than those given in literature for the electronic state (1)^{3}Σ^{−} and smaller for the state (2)^{3}Π. The investigated values of the rotational constant B_{e} in literature are in very good agreement with our calculated values for the 2 electronic states X^{3}Π and (1)^{3}Σ^{−} and larger for the (2)^{3}Π state. The calculated value of the energy T_{e} with respect to the ground state is in an acceptable agreement with the theoretical data given in literature. From this agreement between our investigated data and those calculated in literature we can pretend the accuracy of the new constants obtained for these investigated new electronic excited states.

The electric dipole moment function R_{e}(r) of a molecule is given by:

where

At large internuclear distances, the dipole moment of all the investigated electronic states either tends to a small constant indicating a nearly covalent character of the corresponding state or it smoothly approaches zero which is theoretically the correct behavior for a molecule that dissociates into natural fragments.

In the present work, ab initio investigation for 17 low-lying electronic states in the representation ^{2s+1}Λ^{(+/−)} of the

BP molecule was computed via CASSCF/MRSDCI methods for the electronic excited states. The potential energy curves, the electronic energy with respect to the ground state T_{e}, the harmonic frequency ω_{e}, the internuclear distance R_{e} have been calculated along with the rotational constant B_{e}. The comparisons of the present results with the available values in the literature show an overall a very good agreement. To the best of our knowledge, 14 new electronic states have been investigated for the first time through this work. With the recent interest on this molecule through, the present study of these new excited electronic states may assist in searching for bound states of the BP molecule, which leads to more investigation of new experimental works on this molecule.

MahdiMansour,NaylaEl-Kork,MahmoudKorek, (2015) Theoretical Study of the Triplet Electronic States of the BP Molecule. Journal of Modern Physics,06,1156-1161. doi: 10.4236/jmp.2015.68119