Bound-state energy spectrum and thermochemical functions of the deformed Schiöberg oscillator

In this study, a diatomic molecule interacting potential such as the deformed Schiöberg oscillator (DSO) have been applied to diatomic systems. By solving the Schrödinger equation with the DSO, analytical equations for energy eigenvalues, molar entropy, molar enthalpy, molar Gibbs free energy and constant pressure molar heat capacity are obtained. The obtained equations were used to analyze the physical properties of diatomic molecules. With the aid of the DSO, the percentage average absolute deviation (PAAD) of computed data from the experimental data of the 7Li2 (2 3Πg), NaBr (X 1Σ+), KBr (X 1Σ+) and KRb (B 1Π) molecules are 1.3319%, 0.2108%, 0.2359% and 0.8841%, respectively. The PAAD values obtained by employing the equations of molar entropy, scaled molar enthalpy, scaled molar Gibbs free energy and isobaric molar heat capacity are 1.2919%, 1.5639%, 1.5957% and 2.4041%, respectively, from the experimental data of the KBr (X 1Σ+) molecule. The results for the potential energies, bound-state energy spectra, and thermodynamic functions are in good agreement with the literature on diatomic molecules.

The solution canonical partition function is a prelude to obtaining statistical-mechanical models (or analytical equations) for the calculation of thermo-chemical properties of gaseous molecules.The partition function takes into account; the vibrational, rotational and translational effects of the diatomic system.Analytical equations for the prediction of the molar entropy (S), enthalpy (H), Gibbs free energy (H), and isobaric heat capacity (C p ) exist in the literature, some examples can be found in Refs.  . Diffeent potential functions have been employed in the literature to construct analytical model equations 6,[59][60][61][62][63][64][65][66] .
The present study is centered on the Schiöberg potential energy function.Previously, the bound-state solutions of the Schrödinger and Dirac equations have been obtained with the Schiöberg potential 67,68 .Using the Varshni conditions 6 , Wang and coworkers demonstrated the equivalence of the Manning-Rosen, Deng-Fan and Schiöberg potentials 64 .The Schiöberg oscillator incorporates three independent input parameters viz D e , r e and ω e .
In the quest to model an efficient version of the Schiöberg oscillator, the authors in Ref. 69 employed the transformation r → r−r 0 and the Varshni conditions 6 to construct the reparameterized Schiöberg potential.The reparameterized Schiöberg oscillator is expected to encapsulate four independent input parameters: D e , r e , ω e and α e , nevertheless, the explicit form of the parameter r 0 was not deduced.Many diatomic molecule oscillators have been used by physicists and chemists to predict the thermochemical properties of gaseous molecules 6,55,59,[61][62][63][64][65] .However, for this purpose, the deformed Schiöberg potential has not been considered in the literature.It must be emphasized that q-deforming a potential energy function and subsequently subjecting it to the Varshni conditions for a diatomic molecule potential yields an equivalent model to the reparameterized version 35 .For this reason, the present study primary objectives are to obtain the energy spectra and thermochemical functions of the deformed Schiöberg oscillator.The remaining parts of the paper is organized as follows: In section "Construction of the DSO", the deformed Schiöberg oscillator is constructed.In section "Equation for the energy spectra of the DSO", explicit equation for the energy spectra is derived.Thermochemical functions are obtained in section "Thermochemical functions of the DSO".The results of numerical calculations are presented in section "Results and discussion".A brief conclusion of the work is given in section "Conclusions".

Construction of the DSO
In this section, the deformed Schiöberg oscillator (DSO) is constructed by employing the Varshni conditions 6 .The suggested model potential is given by where, coth q (αr) = cosh q (αr)/sinh q (αr), cosh q (αr) = ½ (e αr + e −αr ), sinh q (αr) = ½ (e αr −e −αr ), r is the interparticle separation, U 0 is the depth of the potential well, q, α and σ are potential parameters.Evidently, (1) is the q-deformed version given in Ref. 64 .The main difference between Eq. (1) and expression (1) of Ref. 70 lies in the functional forms of the two models.
Equation ( 1) is a diatomic molecule oscillator if it satisfies the following conditions 6 where the prime in (2) denotes the derivative with respect to r, the speed of light is designated c, and μ is the reduced mass of a molecule.Inserting Eq. ( 1) into each of the expressions in (2) gives 2 , and γ = αr e .The next step is to determine the potential screening parameter, α.The α e -ω e relationship given in publication 64 can be used, viz where B e = ħ/4πcM 0 r e 2 , ħ = h/2π, h being the Planck constant.U″(r e ) and U‴(r e ) are obtained from Eq. ( 1) as Putting Eq. ( 5) into (4) and simplifying leads to

Equation for the energy spectra of the DSO
In this section, an analytical equation for the energy spectra is derived by solving the radial SE confined by the DSO.Different analytical methods for solving the SE exist in the literature [22][23][24][25][26][27][28] .However, owing to the simplicity of the parametric Nikiforov-Uvarov (PNU) technique 27 , it is considered in this work.

A brief outline of the PNU method
The PNU method gives that with the aid of a suitable coordinate transformation, a second-order differential equation of the hypergeometric-type can be expressed as 27 (1) (2) where α j (j = 0, 1, 2) are constant coefficients, n = 0, 1, 2, … is the vibrational (or principal) quantum number and ℓ = 0, 1, 2, … is the rotational (or orbital momentum) quantum number.The quantization condition leading to energy spectra is written as 27 where

Analytical equation for the energy levels of the DSO by the PNU method
The radial SE for a particle of mass M 0 moving in a radial potential field, U (r) is given by where J = ℓ (ℓ + 1) is the angular momentum of the system, u nℓ (r) is the radial wave function and E nℓ is the bound-state energy eigenvalue.Owing to the presence of the factor r -2 in the centrifugal term, expression (10)  has no exact solution with the potential (1), except for the special case where ℓ = 0 (the pure vibrational state).

Scientific
The maximum vibrational quantum number is deduced from the expression E′ n (n max ) = 0, substituting (18) into this expression gives n max is essentially a positive integer, which is the value of n at which the energy of the system is a maximum.

Thermochemical functions of the DSO
Having obtained the equation for vibrational state energies, in this section, some important analytical models for the prediction of thermochemical properties of substances are developed for the DSO.The canonical partition function from which the thermodynamic expressions are deduced is first derived.The canonical partition function is written as Z (T) = Z vib Z rot Z tra , where T is the temperature of the system, Z vib , Z rot , and Z tra are the vibrational, rotational and translational partition functions, respectively 44,55 .The vibrational partition function depends on the oscillator used to model the diatomic system, it is given as 34 where β = 1/(k B T), k B is the Boltzmann constant.Putting Eq. ( 18) into (20) gives where The series in ( 21) can be evaluated with the help of the modified Poisson summation formula 72 .The modified Poisson summation approach is used here because it is simple to implement and has yielded very accurate results with many oscillator models such as those in Refs. 35,38,73,74.Other methods for evaluating the vibrational partition function including the phase space sampling method and the Euler-Maclaurin summation approach are given in Refs. 75,76.Based on the modified Poisson summation formula, one can write 72 Substituting the second expression in (22) into the right-hand side of (23) and expanding out the summation gives where . The last-two terms in (24) include quantum correction terms.For the moderate to high temperature range of diatomic systems, the quantum correction terms are small and can be ignored.Therefore, expression ( 24) is recast as Using the substitution z = ς {y + δ−κ/(y + δ)}, followed by the mapping x = (z 2 + 2ςκ 2 ) ½ to evaluate the integral, the summation in ( 25) is obtained as Thus, inserting ( 26) into (21), the vibrational partition function is obtained in compact form as where Based on the formalism of the rigid-rotor approximation for diatomic molecules, the rotational and translational components of the partition function are expressed as 36,40,46,50 where V is satisfied by pV = RT, m is the mass of gas molecules enclosed in volume V, the gas pressure is denoted by p, R is the molar gas constant, � rot = 2 /2πµr 2 e k B is the characteristic temperature of the gas.The parameter υ takes the value 2 if the gas is homonuclear, and 1 for heteronuclear gas molecules.Using the expression for the partition function, explicit equations for molar entropy, enthalpy, Gibbs free energy and constant pressure heat capacity are developed for the DSO as follows.

Molar entropy equation for the deformed Schiöberg oscillator
The molar entropy (J mol −1 K −1 ) of the system can be evaluated from the relation 53 Substituting the expression Z (T) = Z vib Z rot Z tra into (31) and using Eqs.( 27), ( 29) and (30) in the result, one obtains where for compactness, the following abbreviation is used

Molar enthalpy model of the DSO
The molar enthalpy (J mol −1 ) of the DSO can be deduced from the expression 54 The substitution Z (T) = Z vib Z rot Z tra and Eqs. ( 27), ( 29) and ( 30) and (34) yields Equation ( 35) can be used to compute molar enthalpy data for diatomic substances.However, to enable the results obtained in this study to be compared with available literature, scaled values of (35) are needed.The scaled molar enthalpy is written as 44,45 (26)

Molar Gibbs free energy of the DSO
Here, the analytical equation for molar Gibbs free energy is derived for the DSO.The Gibbs free energy is given by Replacing ( 34) and ( 31) into (37) gives For the purpose of relating to observed data, the scaled Gibbs free energy is defined as 44,45 Isobaric molar specific heat capacity model of the DSO The constant pressure (isobaric) molar heat capacity (in J mol −1 K −1 ) is evaluated from . Substituting expression (35) into this equation gives where Z ′ vib and Z ′′ vib are given by Eqs. ( 33) and ( 41), respectively

Results and discussion
In this section, the equation derived for the energy levels and thermochemical functions are applied to diatomic substances including 7 Li 2 (2 3 Π g ), NaBr (X 1 Σ + ), KBr (X 1 Σ + ) and KRb (B 1 Π) molecules.The model parameters for these molecules are given in Table 1.The experimental values for D e , r e , ω e and α e were obtained from publications [77][78][79] .The values of the potential parameters also listed in Table 1 were computed with Eqs. ( 3) and (6).
To numerically affirm the accuracy of the model equations, the percentage average absolute deviation (PAAD) of the predicted results from the observed data for the molecule is employed as accuracy indicator.The PAAD values are interpreted according to Lippincott condition for the applicability of a model equation.The Lippincott criterion requires that the PAAD value of the predicted data from the observed data is at most 1% of the experimental results.The smaller the PAAD value, better the model equation.The PAAD value is written in compact form as 80 where N p is the count of observed data, X, Y and Z are chosen in relation to the predicted and observed data.

Numerical results for potential energies
Utilizing the spectroscopic parameters in Table 1, Eq. ( 1) is used to generate numerical results for the potential energy U (≡ U min , U max ) for different vales of r (≡ r min , r max ).The results obtained are given in Tables 2, 3, 4 and 5. Available experimental Rydberg-Klein-Rees (RKR) data 77,79 , and the multireference configuration interaction (MRCI) data 78 for the molecules are also included in the tables.The inclusion of the RKR and MRCI data is to Table 1.Model parameters of the diatomic molecules investigated in this study.

Applicability of the Pekeris approximation scheme to diatomic systems
To ascertain the significance of the Pekeris-type approximation model (11) suggested for the centrifugal barrier of the SE, the function F 1 = r −2 is plotted as a function of interparticle separation.On the same scale and axes, the approximation function F 2 = d 1 + d 2 coth q (αr) + d 3 coth q 2 (αr) is also plotted.The graphical plots depicting F 1 and F 2 for the diatomic molecules are shown in Figs. 5, 6, 7 and 8.It is evident from the figures that for the range of r chosen for the interparticle separations, the Pekeris approximation F 2 is a good representation of the observed function F 1 .The implication of the result is that based on the parameters of the diatomic molecules considered in this study, the Pekeris approximation model F 2 could be used to eliminate the function F 1 to analytically solve the SE (10).

Numerical results for pure vibrational state energies
With the aid of Eq. ( 18), pure vibrational state energies are generated for the selected diatomic molecules.The computed results are summarized in Tables 2, 3, 4 and 5. To quantitatively compare the obtained bound-state energies with the experimental RKR results for the molecules, the parameters in Eq. ( 42) are adjusted so that X = Z = RKR and Y = E n .The PAAD values obtained are 1.0956%, 0.2935%, 3.8667% and 1.4629% for the 7 Li 2 (2 3 Π g ), NaBr (X 1 Σ + ), KBr (X 1 Σ + ) and KRb (B 1 Π) molecules, respectively.Therefore, based on the Lippincott requirement for the applicability of a model equation, the present formula for the pure vibrational state energies could satisfactorily predict the experimental data for the NaBr (X 1 Σ + ) molecule, and marginally model the results for 7 Li 2 (2 3 Π g ) and KRb (B 1 Π) molecules.The PAAD value obtained for the KRb (B 1 Π) molecule is relatively high (≈ 4% of the observed data), suggesting that the present energy levels equation could not satisfactorily predict the observed data for the KRb (B 1 Π) molecule.

Investigation of thermochemical properties of diatomic substances
In this section, the thermodynamic functions developed for the DSO are used to analyze the thermochemical properties of pure substances.To substantiate the accuracy of the model equations, numerical data are obtained analytically and the results are compared with the literature on gaseous substances.The experimental results were retrieved from the National Institute of Standards and Technology (NIST) database 81 .The NIST data is available for the gaseous NaBr and KBr molecules only.Thus, our discussions are restricted to these two molecules.PAAD values computed in the temperature range 300-6000 K are used to gauge the accuracy of the model equations.Tables 6 and 7 summarize the data obtained using Eqs.( 32), ( 36), (39) and (40).The NIST data for the molecules are also listed in the tables under the columns (S NIST ), (H NIST ), (G NIST ) and (C pNIST ).Graphical plots of the thermochemical equations versus temperature are represented in Figs. 9, 10, 11 and 12.The corresponding NIST data are also plotted in the figures.Due to the similarity in the figures for the NaBr and KBr molecules, only the plots for NaBr molecule are presented.
Figure 9 shows the graphical representation of the molar entropy against temperature.The figure shows that the predicted molar entropy agrees with the experimental results.To appraise the quality of the molar entropy model, the parameters X, Y, Z in Eq. ( 42) are chosen such that X = Z = S NIST and Z = S.The PAAD values deduced are 0.5401% and 1.2919%, for NaBr and KBr molecules, respectively.The obtained PAAD values are within the Lippincott error limit.This means that molar entropy equation proposed for the DSO could satisfactorily predict the NIST data for the gaseous NaBr and KBr molecules.In the plot shown in Fig. 10, scaled molar enthalpy is plotted as a function of temperature.The agreement between the observed and predicted data is evident in the figure.An estimate of the efficiency of the molar enthalpy model can be obtained by letting X = Z = H NIST and Z = H scaled in Eq. (42).Using the data in Tables 6  and 7, the computed PAAD values are 1.9428% and 1.5639% for the NaBr and KBr molecules, respectively.The PAAD values reveal that the DSO model for the scaled molar enthalpy could marginally predict the experimental results for the gaseous molecules.It is also noted from the tables that as the molecules are excited from moderate to high temperature region, the discrepancy between the predicted and observed data increases.The increased difference could be linked to lowest order approximation used to obtain expression (36).The absence of the quantum correction terms in the molar entropy equation is responsible for PAAD values exceeding 1%.
The variations in molar Gibbs free energy with temperature is graphically represented in Fig. 11.The figure show that the results obtained by analytical computations are in good agreement with the data reported in the NIST database for the gaseous substances.With the help of the data in Tables 6 and 7, the PAAD values obtained are 0.8164% and 1.5957% for the ground state NaBr and KBr molecules, respectively.The obtained PAAD values are deduced by setting X = Z = G NIST , Y = G scaled in (42).Based on the Lippincott condition, it can be inferred that the molar Gibbs free energy model for the DSO could satisfactorily predict the Gibbs free energy of the selected diatomic molecules.
In Fig. 12, the constant pressure molar heat capacity is plotted against the temperature of the molecules.From the figure, it is clear that in the low temperature range, the predicted isobaric molar heat capacity agrees with the experimental data for the molecules.However, in the moderate to high temperature domain, the predicted heat capacity results are smaller, and deviate significantly from the observed data.The reason for the relatively high deviation could be associated with the quantum corrections terms which are absent in Eq. (40).
Taking X = Z = C pNIST , and Y = C p , the PAAD values deduced for the molecules are 2.9770% and 2.4041% for the ground state NaBr and KBr, respectively.The results clearly suggest that the isobaric molar heat capacity could not accurately predict the experimental results for the NaBr and KBr molecules.Nevertheless, the results  www.nature.com/scientificreports/ in the tables suggest that the model could be used to obtain the molar heat capacity of the molecules within the low temperature range.

Conclusions
In this work, the necessary conditions for a diatomic molecule oscillator were used to construct an improved version of the deformed Schiöberg oscillator (DSO).By employing the parametric Nikiforov-Uvarov solution recipe to solve the radial SE with the DSO, analytical expressions for energy spectra and canonical partition function were obtained.Using the obtained partition function, thermodynamic properties such as molar entropy, enthalpy, Gibbs free energy and isobaric heat capacity were developed for the DSO.The obtained equations were used to analyze the physical properties of diatomic substances including 7 Li 2 (2 3 Π g ), NaBr (X 1 Σ + ), KBr (X 1 Σ + ) and KRb (B 1 Π) molecules.The percentage average absolute deviation (PAAD) of the predicted data from the experimental data of the molecules is used as the goodness-of-fit indicator.The PAAD values obtained with the DSO are 1.3319%, 0.2108%, 0.2359% and 0.8841% for the molecules.The equation of bound state energy levels gave PAAD of 1.0956%, 0.2935%, 3.8667% and 1.4629% from the experimental data of the 7 Li 2 (2 3 Π g ), NaBr (X 1 Σ + ), KBr (X 1 Σ + ) and KRb (B 1 Π) molecules.PAAD values were also obtained using the expression for molar entropy, scaled molar enthalpy, scaled molar Gibbs free energy and constant pressure molar heat capacity models.The results obtained for NaBr (X 1 Σ + ) molecule are 0.5401%, 1.9428%, 0.8164% and 2.9770%.The corresponding results for KBr (X 1 Σ + ) are 1.2919%, 1.5639%, 1.5597% and 2.4041% from the NIST data.The results obtained are in good agreement with theoretic data reported in existing literature and available experimental data on diatomic systems.The results obtained in this study could have practical applications in the many fields of physics and engineering such as solid-state physics, chemical physics, chemical engineering and molecular physics.Table 6.Predicted and observed data on molar entropy (J mol −1 K −1 ), reduced molar enthalpy (kJ mol −1 ), reduced molar Gibbs free energy (J mol −1 K −1 ) and constant pressure molar heat capacity (J mol −1 K −1 ) for the NaBr (X 1 Σ + ) molecule.RGFE a : Reduced Gibbs free energy; CPHC b : Constant pressure heat capacity.Predicted and observed data on molar entropy (J mol −1 K −1 ), reduced molar enthalpy (kJ mol −1 ), reduced molar Gibbs free energy (J mol −1 K −1 ) and constant pressure molar heat capacity (J mol −1 K −1 ) for the KBr (X 1 Σ + ) molecule.RGFE a : Reduced Gibbs free energy; CPHC b : Constant pressure heat capacity.

( 36 )
H scaled = H − h 298.15 , (37) G = H −TS. (38) G = − lnZ vib − lnZ rot − lnZ tra .(39) G scaled = − (G − H 298.15 )/T.(40) www.nature.com/scientificreports/allow for comparison of the predicted values of the potential energies with the observed data for the molecules.The variation in potential energy of the molecules as a function of interparticle separation is given in Figs. 1, 2, 3 and 4. The experimental RKR data are also plotted in the figures.The figures show that the computed potential energy of the molecules agree with the experimental data for the molecules.The accuracy of the DSO to model the experimental RKR data can be determined by letting X = RKR, Y = U and Z = D e in Eq. (

Figure 3 .
Figure 3. Modeling of deformed Schiöberg potential with ab initio MRCI interparticle potential energy data for the KBr (X 1 Σ + ) molecule.

Figure 4 .
Figure 4. Modeling of deformed Schiöberg potential with experimental RKR interparticle potential energy data for the KRb (B 1 Π) molecule.

Figure 6 .
Figure 6.Modeling of the Pekeris approximation scheme F2 to the function F 1 for the NaBr (X 1 Σ + ) molecule.

Figure 7 .
Figure 7. Modeling of the Pekeris approximation scheme F2 to the function F 1 for the KBr (X 1 Σ + ) molecule.

Figure 8 .
Figure 8. Modeling of the Pekeris approximation scheme F2 to the function F 1 for the KRb (B 1 Π) molecule.

Figure 10 .
Figure 10.Graphical representation of scaled molar enthalpy versus temperature for the ground state NaBr molecule.

Figure 11 .
Figure 11.Graphical representation of scaled molar Gibbs free energy versus temperature for the ground state NaBr molecule.

Figure 12 .
Figure 12.Graphical representation of isobaric molar heat capacity versus temperature for the ground state NaBr molecule.
h 298.15 is given by(35), it denotes the molar enthalpy of the molecules calculated at temperature of 298.15K and pressure of 0.1 MPa.