Lab Report 9 Polarizability and Basis Set
CHEM 6343 - Advanced Computational Chemistry Lab Report 9 Polarizability and Basis Set Yunwen Tao∗ April 1, 2015 1 ∗ Graduate Student in CATCO group, Southern Methodist University, yunwent[at]smu.edu A Pople basis set example (From http://www.shodor.org/chemviz/basis/teachers/background. html) 1 1 CHEM 6343 - Advanced Computational Chemistry 1 Brief Introduction In this lab, we are going to modify exponent information in two given basis sets according to Speckman’s paper2 , and to check the modifications to the value of dipole momentum and polarizability. According to Spackman, two basis sets 6-311++G(d,p) and cc-pVQZ will be modified after the optimization work done by him. We will do 6 calculations in total in this lab. The first two is done with Restricted Hartree-Fock with STO-3G and 6-31G(d,p) basis sets. Then, another two calculations with 6-311++G(d,p) and cc-pVQZ basis set will be finished. In the end, calculations with modified 6-311++G(d,p) and cc-pVQZ basis sets will be conducted. 2 Computational Details and Methodology 2.1 General Introduction Generally, the calculation is not difficult but deserves patience especially in the modification of exponent values in basis set information. We will use Polar keyword to calculate polarizability in Gaussian. 2.2 Calculation Setting-up In this section, we will give explicit input information for each calculation. 2.2.1 Calculation I - 1 %chk=water1.chk # opt freq hf/sto-3g geom=connectivity polar Title Card Required 0 1 O H H -5.37533823 -0.80245471 -4.41533823 -0.80245471 -5.69579282 0.10248112 0.00000000 0.00000000 0.00000000 1 2 1.0 3 1.0 2 3 2 Mark A. Spackman, Accurate prediction of static dipole polarizabilities with moderately sized basis sets, J. Phys. Chem., 1989, 93 (22), pp 7594-7603 2 CHEM 6343 - Advanced Computational Chemistry 2.2.2 Calculation I - 2 %chk=water2.chk # opt freq hf/6-31G(d,p) geom=connectivity polar Title Card Required 0 1 O H H -5.37533823 -0.80245471 -4.41533823 -0.80245471 -5.69579282 0.10248112 0.00000000 0.00000000 0.00000000 1 2 1.0 3 1.0 2 3 2.2.3 Calculation II - 1 %chk=water3.chk # gfinput opt freq hf/6-311++G(d,p) geom=connectivity polar Title Card Required 0 1 O H H -5.37533823 -0.80245471 -4.41533823 -0.80245471 -5.69579282 0.10248112 0.00000000 0.00000000 0.00000000 1 2 1.0 3 1.0 2 3 Here we use the keyword gfinput to print the information of basis set for later modifications. Here we print out this part of information in output. 1 0 6 1.00 0.000000000000 0.8588500000D+04 0.1895150083D-02 0.1297230000D+04 0.1438590063D-01 0.2992960000D+03 0.7073200310D-01 0.8737710000D+02 0.2400010105D+00 0.2567890000D+02 0.5947970261D+00 0.3740040000D+01 0.2808020123D+00 SP 3 1.00 0.000000000000 S 3 CHEM 6343 - Advanced Computational Chemistry 0.4211750000D+02 0.1138890124D+00 0.3651139738D-01 0.9628370000D+01 0.9208111006D+00 0.2371529830D+00 0.2853320000D+01 -0.3274470358D-02 0.8197019412D+00 SP 1 1.00 0.000000000000 0.9056610000D+00 0.1000000000D+01 0.1000000000D+01 SP 1 1.00 0.000000000000 0.2556110000D+00 0.1000000000D+01 0.1000000000D+01 SP 1 1.00 0.000000000000 0.8450000000D-01 0.1000000000D+01 0.1000000000D+01 D 1 1.00 0.000000000000 0.1292000000D+01 0.1000000000D+01 **** 2 0 S 3 1.00 0.000000000000 0.3386500000D+02 0.2549381454D-01 0.5094790000D+01 0.1903731086D+00 0.1158790000D+01 0.8521614860D+00 S 1 1.00 0.000000000000 0.3258400000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.1027410000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.3600000000D-01 0.1000000000D+01 P 1 1.00 0.000000000000 0.7500000000D+00 0.1000000000D+01 **** 3 0 S 3 1.00 0.000000000000 0.3386500000D+02 0.2549381454D-01 0.5094790000D+01 0.1903731086D+00 0.1158790000D+01 0.8521614860D+00 S 1 1.00 0.000000000000 0.3258400000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.1027410000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.3600000000D-01 0.1000000000D+01 P 1 1.00 0.000000000000 0.7500000000D+00 0.1000000000D+01 **** 2.2.4 Calculation II - 2 %chk=water4.chk 4 CHEM 6343 - Advanced Computational Chemistry # gfinput opt freq hf/cc-pVQZ geom=connectivity polar Title Card Required 0 1 O H H -5.37533823 -0.80245471 -4.41533823 -0.80245471 -5.69579282 0.10248112 0.00000000 0.00000000 0.00000000 1 2 1.0 3 1.0 2 3 Also, in this one, we also print out the information of basis set. S S S S S P P P 1 0 8 1.00 0.000000000000 0.6142000000D+05 0.1555184099D-03 0.9199000000D+04 0.1184405834D-02 0.2091000000D+04 0.6248769097D-02 0.5909000000D+03 0.2559127665D-01 0.1923000000D+03 0.8775669353D-01 0.6932000000D+02 0.2307291002D+00 0.2697000000D+02 0.4428043050D+00 0.1110000000D+02 0.3336804620D+00 7 1.00 0.000000000000 0.9199000000D+04 -0.7858278867D-05 0.5909000000D+03 -0.4745929019D-03 0.1923000000D+03 -0.2159162994D-02 0.6932000000D+02 -0.2375420471D-01 0.2697000000D+02 -0.1019215293D+00 0.1110000000D+02 -0.4532285868D+00 0.4682000000D+01 -0.4847930118D+00 1 1.00 0.000000000000 0.1428000000D+01 0.1000000000D+01 1 1.00 0.000000000000 0.5547000000D+00 0.1000000000D+01 1 1.00 0.000000000000 0.2067000000D+00 0.1000000000D+01 3 1.00 0.000000000000 0.6342000000D+02 0.3132750252D-01 0.1466000000D+02 0.2166542485D+00 0.4459000000D+01 0.8352428422D+00 1 1.00 0.000000000000 0.1531000000D+01 0.1000000000D+01 1 1.00 0.000000000000 5 CHEM 6343 - Advanced Computational Chemistry 0.5302000000D+00 0.1000000000D+01 1 1.00 0.000000000000 0.1750000000D+00 0.1000000000D+01 D 1 1.00 0.000000000000 0.3775000000D+01 0.1000000000D+01 D 1 1.00 0.000000000000 0.1300000000D+01 0.1000000000D+01 D 1 1.00 0.000000000000 0.4440000000D+00 0.1000000000D+01 F 1 1.00 0.000000000000 0.2666000000D+01 0.1000000000D+01 F 1 1.00 0.000000000000 0.8590000000D+00 0.1000000000D+01 G 1 1.00 0.000000000000 0.1846000000D+01 0.1000000000D+01 **** 2 0 S 3 1.00 0.000000000000 0.8264000000D+02 0.2295075779D-01 0.1241000000D+02 0.1755401181D+00 0.2824000000D+01 0.8647035510D+00 S 1 1.00 0.000000000000 0.7977000000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.2581000000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.8989000000D-01 0.1000000000D+01 P 1 1.00 0.000000000000 0.2292000000D+01 0.1000000000D+01 P 1 1.00 0.000000000000 0.8380000000D+00 0.1000000000D+01 P 1 1.00 0.000000000000 0.2920000000D+00 0.1000000000D+01 D 1 1.00 0.000000000000 0.2062000000D+01 0.1000000000D+01 D 1 1.00 0.000000000000 0.6620000000D+00 0.1000000000D+01 F 1 1.00 0.000000000000 0.1397000000D+01 0.1000000000D+01 **** 3 0 S 3 1.00 0.000000000000 0.8264000000D+02 0.2295075779D-01 0.1241000000D+02 0.1755401181D+00 0.2824000000D+01 0.8647035510D+00 S 1 1.00 0.000000000000 P 6 CHEM 6343 - Advanced Computational Chemistry 0.7977000000D+00 0.1000000000D+01 1 1.00 0.000000000000 0.2581000000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.8989000000D-01 0.1000000000D+01 P 1 1.00 0.000000000000 0.2292000000D+01 0.1000000000D+01 P 1 1.00 0.000000000000 0.8380000000D+00 0.1000000000D+01 P 1 1.00 0.000000000000 0.2920000000D+00 0.1000000000D+01 D 1 1.00 0.000000000000 0.2062000000D+01 0.1000000000D+01 D 1 1.00 0.000000000000 0.6620000000D+00 0.1000000000D+01 F 1 1.00 0.000000000000 0.1397000000D+01 0.1000000000D+01 **** S 2.2.5 Calculation III - 1 %chk=water3_modify.chk # opt freq hf/gen geom=connectivity polar Title Card Required 0 1 O H H -5.37533823 -0.80245471 -4.41533823 -0.80245471 -5.69579282 0.10248112 0.00000000 0.00000000 0.00000000 1 2 1.0 3 1.0 2 3 1 0 6 1.00 0.000000000000 0.8588500000D+04 0.1895150083D-02 0.1297230000D+04 0.1438590063D-01 0.2992960000D+03 0.7073200310D-01 0.8737710000D+02 0.2400010105D+00 0.2567890000D+02 0.5947970261D+00 0.3740040000D+01 0.2808020123D+00 SP 3 1.00 0.000000000000 0.4211750000D+02 0.1138890124D+00 0.3651139738D-01 0.9628370000D+01 0.9208111006D+00 0.2371529830D+00 S 7 CHEM 6343 - Advanced Computational Chemistry 0.2853320000D+01 -0.3274470358D-02 0.8197019412D+00 1 1.00 0.000000000000 0.9056610000D+00 0.1000000000D+01 0.1000000000D+01 SP 1 1.00 0.000000000000 0.2556110000D+00 0.1000000000D+01 0.1000000000D+01 S 1 1.00 0.000000000000 0.6800000000D-01 0.1000000000D+01 0.1000000000D+01 D 1 1.00 0.000000000000 0.0165000000D+01 0.1000000000D+01 **** 2 0 S 3 1.00 0.000000000000 0.3386500000D+02 0.2549381454D-01 0.5094790000D+01 0.1903731086D+00 0.1158790000D+01 0.8521614860D+00 S 1 1.00 0.000000000000 0.3258400000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.1027410000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.6800000000D-01 0.1000000000D+01 P 1 1.00 0.000000000000 0.07300000000D+00 0.1000000000D+01 **** 3 0 S 3 1.00 0.000000000000 0.3386500000D+02 0.2549381454D-01 0.5094790000D+01 0.1903731086D+00 0.1158790000D+01 0.8521614860D+00 S 1 1.00 0.000000000000 0.3258400000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.1027410000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.6800000000D-01 0.1000000000D+01 P 1 1.00 0.000000000000 0.07300000000D+00 0.1000000000D+01 **** SP 2.2.6 Calculation III - 2 %chk=water4_modify.chk # opt freq hf/gen geom=connectivity polar Title Card Required 8 CHEM 6343 - Advanced Computational Chemistry 0 1 O H H -5.37533823 -0.80245471 -4.41533823 -0.80245471 -5.69579282 0.10248112 1 2 1.0 3 1.0 2 3 S S S S S P P P P D D 1 0 8 1.00 0.000000000000 0.6142000000D+05 0.1555184099D-03 0.9199000000D+04 0.1184405834D-02 0.2091000000D+04 0.6248769097D-02 0.5909000000D+03 0.2559127665D-01 0.1923000000D+03 0.8775669353D-01 0.6932000000D+02 0.2307291002D+00 0.2697000000D+02 0.4428043050D+00 0.1110000000D+02 0.3336804620D+00 7 1.00 0.000000000000 0.9199000000D+04 -0.7858278867D-05 0.5909000000D+03 -0.4745929019D-03 0.1923000000D+03 -0.2159162994D-02 0.6932000000D+02 -0.2375420471D-01 0.2697000000D+02 -0.1019215293D+00 0.1110000000D+02 -0.4532285868D+00 0.4682000000D+01 -0.4847930118D+00 1 1.00 0.000000000000 0.1428000000D+01 0.1000000000D+01 1 1.00 0.000000000000 0.5547000000D+00 0.1000000000D+01 1 1.00 0.000000000000 0.2067000000D+00 0.1000000000D+01 3 1.00 0.000000000000 0.6342000000D+02 0.3132750252D-01 0.1466000000D+02 0.2166542485D+00 0.4459000000D+01 0.8352428422D+00 1 1.00 0.000000000000 0.1531000000D+01 0.1000000000D+01 1 1.00 0.000000000000 0.5302000000D+00 0.1000000000D+01 1 1.00 0.000000000000 0.1750000000D+00 0.1000000000D+01 1 1.00 0.000000000000 0.3775000000D+01 0.1000000000D+01 1 1.00 0.000000000000 9 0.00000000 0.00000000 0.00000000 CHEM 6343 - Advanced Computational Chemistry 0.1300000000D+01 0.1000000000D+01 1 1.00 0.000000000000 0.4440000000D+00 0.1000000000D+01 F 1 1.00 0.000000000000 0.2666000000D+01 0.1000000000D+01 F 1 1.00 0.000000000000 0.8590000000D+00 0.1000000000D+01 **** 2 0 S 3 1.00 0.000000000000 0.8264000000D+02 0.2295075779D-01 0.1241000000D+02 0.1755401181D+00 0.2824000000D+01 0.8647035510D+00 S 1 1.00 0.000000000000 0.7977000000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.2581000000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.8989000000D-01 0.1000000000D+01 P 1 1.00 0.000000000000 0.2292000000D+01 0.1000000000D+01 P 1 1.00 0.000000000000 0.8380000000D+00 0.1000000000D+01 P 1 1.00 0.000000000000 0.2920000000D+00 0.1000000000D+01 D 1 1.00 0.000000000000 0.2062000000D+01 0.1000000000D+01 D 1 1.00 0.000000000000 0.6620000000D+00 0.1000000000D+01 F 1 1.00 0.000000000000 0.1397000000D+01 0.1000000000D+01 **** 3 0 S 3 1.00 0.000000000000 0.8264000000D+02 0.2295075779D-01 0.1241000000D+02 0.1755401181D+00 0.2824000000D+01 0.8647035510D+00 S 1 1.00 0.000000000000 0.7977000000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.2581000000D+00 0.1000000000D+01 S 1 1.00 0.000000000000 0.8989000000D-01 0.1000000000D+01 P 1 1.00 0.000000000000 0.2292000000D+01 0.1000000000D+01 P 1 1.00 0.000000000000 D 10 CHEM 6343 - Advanced Computational Chemistry 0.8380000000D+00 0.1000000000D+01 1 1.00 0.000000000000 0.2920000000D+00 0.1000000000D+01 D 1 1.00 0.000000000000 0.2062000000D+01 0.1000000000D+01 D 1 1.00 0.000000000000 0.6620000000D+00 0.1000000000D+01 F 1 1.00 0.000000000000 0.1397000000D+01 0.1000000000D+01 **** P 3 Data In this section, we listed all data for number of basis functions, primitive gaussians, total dipole moments and polarizabilities. Table 1: Data for number of basis functions, primitive gaussians, total energy and dipole moment. Basis set STO-3G 6-31G(d,p) 6-311++G(d,p) Modified 6-311++G(d,p) cc-pVQZ Modified cc-pVQZ Basis function # Primitive Gaussian # Total energy (a.u.) Dipole moment (Debye) 7 25 36 33 115 106 21 42 54 51 163 149 -74.9659011708 -76.0236149302 -76.0534234741 -76.0245014252 -76.0655184122 -76.0655088433 1.7094 2.1485 2.1968 2.0615 1.9660 1.9658 Table 2: Data for polarizability in the unit of Bohr3 Basis set STO-3G 6-31G(d,p) 6-311++G(d,p) Modified 6-311++G(d,p) cc-pVQZ Modified cc-pVQZ Experimental data αxx αyy αzz 0.040 2.931 5.502 7.230 6.074 6.072 10.399 5.506 6.769 7.421 8.941 8.184 8.183 11.231 2.565 4.906 5.853 7.905 7.234 7.233 10.788 11 CHEM 6343 - Advanced Computational Chemistry 4 Conclusion In this lab, we could easily see that Modified 6-311++G(d,p) did the best job in calculating polarizability although it has nearly 30% error. Because the modification to 6-311++G(d,p) explicitly includes altering the exponents if the d polarization function for oxygen and the p polarization function for hydrogen as well as changing a diffuse sp function for oxygen to a diffuse s function and altering the exponents of this s function for both oxygen and hydrogen. The resulting basis set is called 6-31G(+sd,+sp). However, it seems that for cc-pVQZ basis set which is quite larger than 6-311++G(d,p), after the modification, the properties and energies calculated do not change so much. Maybe the reason is that larger basis sets have more basis functions, and changing just a few of them can not matter so much. 12
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