From owner-chemistry@ccl.net Tue Jun 28 15:16:00 2022 From: "Andrew DeYoung andrewdaviddeyoung^_^gmail.com" To: CCL Subject: CCL:G: Question about phosphorus in 6-31G basis set Message-Id: <-54737-220628135923-31763-uLANVhV9mEzSi0yiQyxRtQ],[server.ccl.net> X-Original-From: Andrew DeYoung Content-Type: multipart/alternative; boundary="00000000000080345305e285cb3d" Date: Tue, 28 Jun 2022 13:59:05 -0400 MIME-Version: 1.0 Sent to CCL by: Andrew DeYoung [andrewdaviddeyoung^-^gmail.com] --00000000000080345305e285cb3d Content-Type: text/plain; charset="UTF-8" Hi, I am running a geometry optimization in Gaussian 16. One of the ions in my system contains a phosphorus atom. As an inexpensive starting point, I chose the HF/6-31G level of theory, which is built into Gaussian: # Opt HF/6-31G Gaussian gives me this warning: " Warning! P atom 19 may be hypervalent but has no d functions." So, I went to the Basis Set Exchange and took a look at the form of the 6-31 basis set for phosphorus ( https://www.basissetexchange.org/basis/6-31g/format/gaussian94/?version=1&elements=15 ) and found that, indeed, there are no d functions: !---------------------------------------------------------------------- ! Basis Set Exchange ! Version v0.9 ! https://www.basissetexchange.org !---------------------------------------------------------------------- ! Basis set: 6-31G ! Description: 6-31G valence double-zeta ! Role: orbital ! Version: 1 (Data from Gaussian 09/GAMESS) !---------------------------------------------------------------------- P 0 S 6 1.00 0.1941330000D+05 0.1851598923D-02 0.2909420000D+04 0.1420619174D-01 0.6613640000D+03 0.6999945928D-01 0.1857590000D+03 0.2400788603D+00 0.5919430000D+02 0.4847617180D+00 0.2003100000D+02 0.3351998050D+00 SP 6 1.00 0.3394780000D+03 -0.2782170105D-02 0.4564616191D-02 0.8101010000D+02 -0.3604990135D-01 0.3369357188D-01 0.2587800000D+02 -0.1166310044D+00 0.1397548834D+00 0.9452210000D+01 0.9683280364D-01 0.3393617168D+00 0.3665660000D+01 0.6144180231D+00 0.4509206237D+00 0.1467460000D+01 0.4037980152D+00 0.2385858009D+00 SP 3 1.00 0.2156230000D+01 -0.2529241139D+00 -0.1776531273D-01 0.7489970000D+00 0.3285184468D-01 0.2740581964D+00 0.2831450000D+00 0.1081254762D+01 0.7854215630D+00 SP 1 1.00 0.9983170000D-01 0.1000000000D+01 0.1000000000D+01 **** On the other hand, 6-31G*, alias 6-31G(d), not surprisingly, does have a d function ( https://www.basissetexchange.org/basis/6-31g_st_/format/gaussian94/?version=1&elements=15 ): !---------------------------------------------------------------------- ! Basis Set Exchange ! Version v0.9 ! https://www.basissetexchange.org !---------------------------------------------------------------------- ! Basis set: 6-31G* ! Description: 6-31G + polarization on heavy atoms ! Role: orbital ! Version: 1 (Data from Gaussian 09/GAMESS) !---------------------------------------------------------------------- P 0 S 6 1.00 0.1941330000D+05 0.1851598923D-02 0.2909420000D+04 0.1420619174D-01 0.6613640000D+03 0.6999945928D-01 0.1857590000D+03 0.2400788603D+00 0.5919430000D+02 0.4847617180D+00 0.2003100000D+02 0.3351998050D+00 SP 6 1.00 0.3394780000D+03 -0.2782170105D-02 0.4564616191D-02 0.8101010000D+02 -0.3604990135D-01 0.3369357188D-01 0.2587800000D+02 -0.1166310044D+00 0.1397548834D+00 0.9452210000D+01 0.9683280364D-01 0.3393617168D+00 0.3665660000D+01 0.6144180231D+00 0.4509206237D+00 0.1467460000D+01 0.4037980152D+00 0.2385858009D+00 SP 3 1.00 0.2156230000D+01 -0.2529241139D+00 -0.1776531273D-01 0.7489970000D+00 0.3285184468D-01 0.2740581964D+00 0.2831450000D+00 0.1081254762D+01 0.7854215630D+00 SP 1 1.00 0.9983170000D-01 0.1000000000D+01 0.1000000000D+01 D 1 1.00 0.5500000000D+00 1.0000000 **** I am new to quantum chemical calculations, so please forgive me if this is an extremely basic question with an obvious answer. Why doesn't phosphorus have d functions in 6-31G, while atoms such as potassium and calcium do? (See, for example, https://www.basissetexchange.org/basis/6-31g/format/gaussian94/?version=1&elements=19,20 .) I realize that phosphorus ([Ne] 3s^2 3p^3) doesn't have d electrons, but neither do potassium ([Ar] 4s^1) or calcium ([Ar] 4s^2) and yet their 6-31G basis functions do include d functions ([Ar] = [Ne] 3s^2 3p^6 and [Ne] = 1s^2 2s^2 2p^6). Thanks so much for your help, and thanks for your patience with a probably very basic question, Andrew --00000000000080345305e285cb3d Content-Type: text/html; charset="UTF-8" Content-Transfer-Encoding: quoted-printable
Hi,

I am running a geomet= ry optimization in Gaussian 16.=C2=A0 One of the ions in my system contains= a phosphorus atom.=C2=A0 As an inexpensive starting point, I chose the HF/= 6-31G level of theory, which is built into Gaussian:

# Opt HF/6-31G

Gaussian gives me this warning:<= /div>
" Warning!=C2=A0 P =C2=A0atom =C2=A0 19 may be hypervalent b= ut has no d functions."

So, I went to the Bas= is Set Exchange and took a look at the form of the 6-31 basis set for=20 phosphorus=20 ( https://www.basissetexch= ange.org/basis/6-31g/format/gaussian94/?version=3D1&elements=3D15 )= and found that, indeed, there are no d functions:

!--------------= --------------------------------------------------------
! Basis Set Exc= hange
! Version v0.9
! https://www.basissetexchange.org
!-----------------= -----------------------------------------------------
! =C2=A0 Basis set= : 6-31G
! Description: 6-31G valence double-zeta
! =C2=A0 =C2=A0 =C2= =A0 =C2=A0Role: orbital
! =C2=A0 =C2=A0 Version: 1 =C2=A0(Data from Gaus= sian 09/GAMESS)
!-------------------------------------------------------= ---------------

P =C2=A0 =C2=A0 0
S =C2=A0 =C2=A06 =C2=A0 1.00=C2=A0 =C2=A0 =C2=A0 0.1941330000D+05 =C2=A0 =C2=A0 =C2=A0 0.1851598923D-0= 2
=C2=A0 =C2=A0 =C2=A0 0.2909420000D+04 =C2=A0 =C2=A0 =C2=A0 0.142061917= 4D-01
=C2=A0 =C2=A0 =C2=A0 0.6613640000D+03 =C2=A0 =C2=A0 =C2=A0 0.69999= 45928D-01
=C2=A0 =C2=A0 =C2=A0 0.1857590000D+03 =C2=A0 =C2=A0 =C2=A0 0.2= 400788603D+00
=C2=A0 =C2=A0 =C2=A0 0.5919430000D+02 =C2=A0 =C2=A0 =C2=A0= 0.4847617180D+00
=C2=A0 =C2=A0 =C2=A0 0.2003100000D+02 =C2=A0 =C2=A0 = =C2=A0 0.3351998050D+00
SP =C2=A0 6 =C2=A0 1.00
=C2=A0 =C2=A0 =C2=A0 = 0.3394780000D+03 =C2=A0 =C2=A0 =C2=A0-0.2782170105D-02 =C2=A0 =C2=A0 =C2=A0= 0.4564616191D-02
=C2=A0 =C2=A0 =C2=A0 0.8101010000D+02 =C2=A0 =C2=A0 = =C2=A0-0.3604990135D-01 =C2=A0 =C2=A0 =C2=A0 0.3369357188D-01
=C2=A0 =C2= =A0 =C2=A0 0.2587800000D+02 =C2=A0 =C2=A0 =C2=A0-0.1166310044D+00 =C2=A0 = =C2=A0 =C2=A0 0.1397548834D+00
=C2=A0 =C2=A0 =C2=A0 0.9452210000D+01 =C2= =A0 =C2=A0 =C2=A0 0.9683280364D-01 =C2=A0 =C2=A0 =C2=A0 0.3393617168D+00=C2=A0 =C2=A0 =C2=A0 0.3665660000D+01 =C2=A0 =C2=A0 =C2=A0 0.6144180231D+0= 0 =C2=A0 =C2=A0 =C2=A0 0.4509206237D+00
=C2=A0 =C2=A0 =C2=A0 0.146746000= 0D+01 =C2=A0 =C2=A0 =C2=A0 0.4037980152D+00 =C2=A0 =C2=A0 =C2=A0 0.23858580= 09D+00
SP =C2=A0 3 =C2=A0 1.00
=C2=A0 =C2=A0 =C2=A0 0.2156230000D+01 = =C2=A0 =C2=A0 =C2=A0-0.2529241139D+00 =C2=A0 =C2=A0 =C2=A0-0.1776531273D-01=
=C2=A0 =C2=A0 =C2=A0 0.7489970000D+00 =C2=A0 =C2=A0 =C2=A0 0.3285184468= D-01 =C2=A0 =C2=A0 =C2=A0 0.2740581964D+00
=C2=A0 =C2=A0 =C2=A0 0.283145= 0000D+00 =C2=A0 =C2=A0 =C2=A0 0.1081254762D+01 =C2=A0 =C2=A0 =C2=A0 0.78542= 15630D+00
SP =C2=A0 1 =C2=A0 1.00
=C2=A0 =C2=A0 =C2=A0 0.9983170000D-= 01 =C2=A0 =C2=A0 =C2=A0 0.1000000000D+01 =C2=A0 =C2=A0 =C2=A0 0.1000000000D= +01
****

On the other hand, 6-31G*, alias = 6-31G(d), not surprisingly, does have a d function ( https://www.basissetexchange.org/basis/6-31g= _st_/format/gaussian94/?version=3D1&elements=3D15 ):

=
!---------------------------------------------------------------= -------
! Basis Set Exchange
! Version v0.9
! https://www.basissetexchange.org=
!------------------------------------------------------------------= ----
! =C2=A0 Basis set: 6-31G*
! Description: 6-31G + polarization o= n heavy atoms
! =C2=A0 =C2=A0 =C2=A0 =C2=A0Role: orbital
! =C2=A0 =C2= =A0 Version: 1 =C2=A0(Data from Gaussian 09/GAMESS)
!-------------------= ---------------------------------------------------

P =C2=A0 =C2=A0 = 0
S =C2=A0 =C2=A06 =C2=A0 1.00
=C2=A0 =C2=A0 =C2=A0 0.1941330000D+05 = =C2=A0 =C2=A0 =C2=A0 0.1851598923D-02
=C2=A0 =C2=A0 =C2=A0 0.2909420000D= +04 =C2=A0 =C2=A0 =C2=A0 0.1420619174D-01
=C2=A0 =C2=A0 =C2=A0 0.6613640= 000D+03 =C2=A0 =C2=A0 =C2=A0 0.6999945928D-01
=C2=A0 =C2=A0 =C2=A0 0.185= 7590000D+03 =C2=A0 =C2=A0 =C2=A0 0.2400788603D+00
=C2=A0 =C2=A0 =C2=A0 0= .5919430000D+02 =C2=A0 =C2=A0 =C2=A0 0.4847617180D+00
=C2=A0 =C2=A0 =C2= =A0 0.2003100000D+02 =C2=A0 =C2=A0 =C2=A0 0.3351998050D+00
SP =C2=A0 6 = =C2=A0 1.00
=C2=A0 =C2=A0 =C2=A0 0.3394780000D+03 =C2=A0 =C2=A0 =C2=A0-0= .2782170105D-02 =C2=A0 =C2=A0 =C2=A0 0.4564616191D-02
=C2=A0 =C2=A0 =C2= =A0 0.8101010000D+02 =C2=A0 =C2=A0 =C2=A0-0.3604990135D-01 =C2=A0 =C2=A0 = =C2=A0 0.3369357188D-01
=C2=A0 =C2=A0 =C2=A0 0.2587800000D+02 =C2=A0 =C2= =A0 =C2=A0-0.1166310044D+00 =C2=A0 =C2=A0 =C2=A0 0.1397548834D+00
=C2=A0= =C2=A0 =C2=A0 0.9452210000D+01 =C2=A0 =C2=A0 =C2=A0 0.9683280364D-01 =C2= =A0 =C2=A0 =C2=A0 0.3393617168D+00
=C2=A0 =C2=A0 =C2=A0 0.3665660000D+01= =C2=A0 =C2=A0 =C2=A0 0.6144180231D+00 =C2=A0 =C2=A0 =C2=A0 0.4509206237D+0= 0
=C2=A0 =C2=A0 =C2=A0 0.1467460000D+01 =C2=A0 =C2=A0 =C2=A0 0.403798015= 2D+00 =C2=A0 =C2=A0 =C2=A0 0.2385858009D+00
SP =C2=A0 3 =C2=A0 1.00
= =C2=A0 =C2=A0 =C2=A0 0.2156230000D+01 =C2=A0 =C2=A0 =C2=A0-0.2529241139D+00= =C2=A0 =C2=A0 =C2=A0-0.1776531273D-01
=C2=A0 =C2=A0 =C2=A0 0.7489970000= D+00 =C2=A0 =C2=A0 =C2=A0 0.3285184468D-01 =C2=A0 =C2=A0 =C2=A0 0.274058196= 4D+00
=C2=A0 =C2=A0 =C2=A0 0.2831450000D+00 =C2=A0 =C2=A0 =C2=A0 0.10812= 54762D+01 =C2=A0 =C2=A0 =C2=A0 0.7854215630D+00
SP =C2=A0 1 =C2=A0 1.00<= br>=C2=A0 =C2=A0 =C2=A0 0.9983170000D-01 =C2=A0 =C2=A0 =C2=A0 0.1000000000D= +01 =C2=A0 =C2=A0 =C2=A0 0.1000000000D+01
D =C2=A0 =C2=A01 =C2=A0 1.00=C2=A0 =C2=A0 =C2=A0 0.5500000000D+00 =C2=A0 =C2=A0 =C2=A0 1.0000000
*= ***

I am new to quantum chemical calculations, so = please forgive me if this is an extremely basic question with an obvious an= swer.=C2=A0 Why doesn't phosphorus have d functions in 6-31G, while ato= ms such as potassium and calcium do?=C2=A0 (See, for example, https://www.basissetexchange.org/bas= is/6-31g/format/gaussian94/?version=3D1&elements=3D19,20 .)=C2=A0 I= realize that phosphorus ([Ne] 3s^2 3p^3) doesn't have d electrons, but= neither do potassium ([Ar] 4s^1) or calcium ([Ar] 4s^2) and yet their 6-31= G basis functions do include d functions ([Ar] =3D [Ne] 3s^2 3p^6 and=20 [Ne] =3D 1s^2 2s^2 2p^6).=C2=A0

Thanks so muc= h for your help, and thanks for your patience with a probably very basic qu= estion,
Andrew
--00000000000080345305e285cb3d-- From owner-chemistry@ccl.net Tue Jun 28 21:58:01 2022 From: "Cory Pye Cory.Pye+/-smu.ca" To: CCL Subject: CCL:G: Question about phosphorus in 6-31G basis set Message-Id: <-54738-220628214017-10719-EyKEL0Uy92B9fDZaKfwoew(!)server.ccl.net> X-Original-From: Cory Pye Content-Language: en-US Content-Type: multipart/alternative; boundary="_000_YT1PR01MB2873060073D18E5BBE9C1BADF8BB9YT1PR01MB2873CANP_" Date: Wed, 29 Jun 2022 01:40:06 +0000 MIME-Version: 1.0 Sent to CCL by: Cory Pye [Cory.Pye^smu.ca] --_000_YT1PR01MB2873060073D18E5BBE9C1BADF8BB9YT1PR01MB2873CANP_ Content-Type: text/plain; charset="us-ascii" Content-Transfer-Encoding: quoted-printable Andrew, I believe that it is because the developers of the basis set strive for a c= onsistent description across each period of the periodic table. I would imagine part of the reason might be that the use of Cartesian D ins= tead of spherical harmonic d might interact with the s-shell because of the= x^2 + y^2 + z^2 combination. The beginning and end members of the series h= ave the same contraction pattern. H-He =3D (3S, 1S) Li-Ne =3D (6S,3SP,1SP) < note here that Li has SP shells even though its el= ectron configuration is [He]2s1 . In order to get contraction coefficients = for the P part of the SP shells for Li and Be, they probably had to optimiz= e them for an excited configuration with at least one electron in the 2p or= bital. Na-Ar =3D (6S,6SP,3SP,1SP) - no occupied d orbitals in any of these element= s. K-Kr =3D (6s,6SP,6SP,3SP,1SP,3D,1D) - the 3d orbitals start filling in here= . In order to get contraction coefficients for the d orbitals for K and Ca,= one would have to optimize these for some excited configuration with at le= ast one electron in a d orbital. -Cory > From: owner-chemistry+cory.pye=3D=3Dsmu.ca~!~ccl.net On Behalf Of Andrew DeYoung andrewdaviddeyoung^_^gma= il.com Sent: Tuesday, June 28, 2022 2:59 PM To: Cory Pye Subject: CCL:G: Question about phosphorus in 6-31G basis set Hi, I am running a geometry optimization in Gaussian 16. One of the ions in my= system contains a phosphorus atom. As an inexpensive starting point, I ch= ose the HF/6-31G level of theory, which is built into Gaussian: # Opt HF/6-31G Gaussian gives me this warning: " Warning! P atom 19 may be hypervalent but has no d functions." So, I went to the Basis Set Exchange and took a look at the form of the 6-3= 1 basis set for phosphorus ( https://www.basissetexchange.org/basis/6-31g/f= ormat/gaussian94/?version=3D1&elements=3D15 ) and= found that, indeed, there are no d functions: !---------------------------------------------------------------------- ! Basis Set Exchange ! Version v0.9 ! https://www.basissetexchange.org !---------------------------------------------------------------------- ! Basis set: 6-31G ! Description: 6-31G valence double-zeta ! Role: orbital ! Version: 1 (Data from Gaussian 09/GAMESS) !---------------------------------------------------------------------- P 0 S 6 1.00 0.1941330000D+05 0.1851598923D-02 0.2909420000D+04 0.1420619174D-01 0.6613640000D+03 0.6999945928D-01 0.1857590000D+03 0.2400788603D+00 0.5919430000D+02 0.4847617180D+00 0.2003100000D+02 0.3351998050D+00 SP 6 1.00 0.3394780000D+03 -0.2782170105D-02 0.4564616191D-02 0.8101010000D+02 -0.3604990135D-01 0.3369357188D-01 0.2587800000D+02 -0.1166310044D+00 0.1397548834D+00 0.9452210000D+01 0.9683280364D-01 0.3393617168D+00 0.3665660000D+01 0.6144180231D+00 0.4509206237D+00 0.1467460000D+01 0.4037980152D+00 0.2385858009D+00 SP 3 1.00 0.2156230000D+01 -0.2529241139D+00 -0.1776531273D-01 0.7489970000D+00 0.3285184468D-01 0.2740581964D+00 0.2831450000D+00 0.1081254762D+01 0.7854215630D+00 SP 1 1.00 0.9983170000D-01 0.1000000000D+01 0.1000000000D+01 **** On the other hand, 6-31G*, alias 6-31G(d), not surprisingly, does have a d = function ( https://www.basissetexchange.org/basis/6-31g_st_/format/gaussian= 94/?version=3D1&elements=3D15 ): !---------------------------------------------------------------------- ! Basis Set Exchange ! Version v0.9 ! https://www.basissetexchange.org !---------------------------------------------------------------------- ! Basis set: 6-31G* ! Description: 6-31G + polarization on heavy atoms ! Role: orbital ! Version: 1 (Data from Gaussian 09/GAMESS) !---------------------------------------------------------------------- P 0 S 6 1.00 0.1941330000D+05 0.1851598923D-02 0.2909420000D+04 0.1420619174D-01 0.6613640000D+03 0.6999945928D-01 0.1857590000D+03 0.2400788603D+00 0.5919430000D+02 0.4847617180D+00 0.2003100000D+02 0.3351998050D+00 SP 6 1.00 0.3394780000D+03 -0.2782170105D-02 0.4564616191D-02 0.8101010000D+02 -0.3604990135D-01 0.3369357188D-01 0.2587800000D+02 -0.1166310044D+00 0.1397548834D+00 0.9452210000D+01 0.9683280364D-01 0.3393617168D+00 0.3665660000D+01 0.6144180231D+00 0.4509206237D+00 0.1467460000D+01 0.4037980152D+00 0.2385858009D+00 SP 3 1.00 0.2156230000D+01 -0.2529241139D+00 -0.1776531273D-01 0.7489970000D+00 0.3285184468D-01 0.2740581964D+00 0.2831450000D+00 0.1081254762D+01 0.7854215630D+00 SP 1 1.00 0.9983170000D-01 0.1000000000D+01 0.1000000000D+01 D 1 1.00 0.5500000000D+00 1.0000000 **** I am new to quantum chemical calculations, so please forgive me if this is = an extremely basic question with an obvious answer. Why doesn't phosphorus= have d functions in 6-31G, while atoms such as potassium and calcium do? = (See, for example, https://www.basissetexchange.org/basis/6-31g/format/gaus= sian94/?version=3D1&elements=3D19,20 .) I= realize that phosphorus ([Ne] 3s^2 3p^3) doesn't have d electrons, but nei= ther do potassium ([Ar] 4s^1) or calcium ([Ar] 4s^2) and yet their 6-31G ba= sis functions do include d functions ([Ar] =3D [Ne] 3s^2 3p^6 and [Ne] =3D = 1s^2 2s^2 2p^6). Thanks so much for your help, and thanks for your patience with a probably = very basic question, Andrew --_000_YT1PR01MB2873060073D18E5BBE9C1BADF8BB9YT1PR01MB2873CANP_ Content-Type: text/html; charset="us-ascii" Content-Transfer-Encoding: quoted-printable

Andrew,

 

I believe that it is because the developers of the b= asis set strive for a consistent description across each period of the peri= odic table.

I would imagine part of the reason might be that the= use of Cartesian D instead of spherical harmonic d might interact with the= s-shell because of the x^2 + y^2 + z^2 combination. The beginning and end = members of the series have the same contraction pattern.

 

H-He =3D (3S, 1S)

Li-Ne =3D (6S,3SP,1SP) < note here that Li has SP= shells even though its electron configuration is [He]2s1 . In order to get= contraction coefficients for the P part of the SP shells for Li and Be, th= ey probably had to optimize them for an excited configuration with at least one electron in the 2p orbital.

Na-Ar =3D (6S,6SP,3SP,1SP) – no occupied d orb= itals in any of these elements.

K-Kr =3D (6s,6SP,6SP,3SP,1SP,3D,1D) – the 3d o= rbitals start filling in here. In order to get contraction coefficients for= the d orbitals for K and Ca, one would have to optimize these for some exc= ited configuration with at least one electron in a d orbital.

 

-Cory

 

From: owner-chemistry+cory.pye=3D=3Dsmu.ca~!~ccl.net <owner-chemistr= y+cory.pye=3D=3Dsmu.ca~!~ccl.net> On Behalf Of Andrew DeYoung andrewdaviddeyoung^_^gmail.com
Sent: Tuesday, June 28, 2022 2:59 PM
To: Cory Pye <Cory.Pye~!~smu.ca>
Subject: CCL:G: Question about phosphorus in 6-31G basis set

 

Hi,

 

I am running a geometry optimization in Gaussian 16.=   One of the ions in my system contains a phosphorus atom.  As an= inexpensive starting point, I chose the HF/6-31G level of theory, which is= built into Gaussian:

 

# Opt HF/6-31G

 

Gaussian gives me this warning:

" Warning!  P  atom   19 may be = hypervalent but has no d functions."

 

So, I went to the Basis Set Exchange and took a look= at the form of the 6-31 basis set for phosphorus ( https://www.basissetexchange.org/basis/6-31g/format/gaussian94/?version=3D1= &elements=3D15 ) and found that, indeed, there are no d functions:<= o:p>


!----------------------------------------------------------------------
! Basis Set Exchange
! Version v0.9
! https://www.basissetexchange.org
!----------------------------------------------------------------------
!   Basis set: 6-31G
! Description: 6-31G valence double-zeta
!        Role: orbital
!     Version: 1  (Data from Gaussian 09/GAMESS)
!----------------------------------------------------------------------

P     0
S    6   1.00
      0.1941330000D+05       0.1851598923D-02=
      0.2909420000D+04       0.1420619174D-01=
      0.6613640000D+03       0.6999945928D-01=
      0.1857590000D+03       0.2400788603D+00=
      0.5919430000D+02       0.4847617180D+00=
      0.2003100000D+02       0.3351998050D+00=
SP   6   1.00
      0.3394780000D+03      -0.2782170105D-02=       0.4564616191D-02
      0.8101010000D+02      -0.3604990135D-01=       0.3369357188D-01
      0.2587800000D+02      -0.1166310044D+00=       0.1397548834D+00
      0.9452210000D+01       0.9683280364D-01=       0.3393617168D+00
      0.3665660000D+01       0.6144180231D+00=       0.4509206237D+00
      0.1467460000D+01       0.4037980152D+00=       0.2385858009D+00
SP   3   1.00
      0.2156230000D+01      -0.2529241139D+00=      -0.1776531273D-01
      0.7489970000D+00       0.3285184468D-01=       0.2740581964D+00
      0.2831450000D+00       0.1081254762D+01=       0.7854215630D+00
SP   1   1.00
      0.9983170000D-01       0.1000000000D+01=       0.1000000000D+01

****

 

On the other hand, 6-31G*, alias 6-31G(d), not surpr= isingly, does have a d function ( https://www.basissetexchange.org/basis/6-31g_st_/format/gaussian94/?version= =3D1&elements=3D15 ):

 

!---------------------------------------------------= -------------------
! Basis Set Exchange
! Version v0.9
! https://www.basissetexchange.org
!----------------------------------------------------------------------
!   Basis set: 6-31G*
! Description: 6-31G + polarization on heavy atoms
!        Role: orbital
!     Version: 1  (Data from Gaussian 09/GAMESS)
!----------------------------------------------------------------------

P     0
S    6   1.00
      0.1941330000D+05       0.1851598923D-02=
      0.2909420000D+04       0.1420619174D-01=
      0.6613640000D+03       0.6999945928D-01=
      0.1857590000D+03       0.2400788603D+00=
      0.5919430000D+02       0.4847617180D+00=
      0.2003100000D+02       0.3351998050D+00=
SP   6   1.00
      0.3394780000D+03      -0.2782170105D-02=       0.4564616191D-02
      0.8101010000D+02      -0.3604990135D-01=       0.3369357188D-01
      0.2587800000D+02      -0.1166310044D+00=       0.1397548834D+00
      0.9452210000D+01       0.9683280364D-01=       0.3393617168D+00
      0.3665660000D+01       0.6144180231D+00=       0.4509206237D+00
      0.1467460000D+01       0.4037980152D+00=       0.2385858009D+00
SP   3   1.00
      0.2156230000D+01      -0.2529241139D+00=      -0.1776531273D-01
      0.7489970000D+00       0.3285184468D-01=       0.2740581964D+00
      0.2831450000D+00       0.1081254762D+01=       0.7854215630D+00
SP   1   1.00
      0.9983170000D-01       0.1000000000D+01=       0.1000000000D+01
D    1   1.00
      0.5500000000D+00       1.0000000
****

 

I am new to quantum chemical calculations, so please= forgive me if this is an extremely basic question with an obvious answer.&= nbsp; Why doesn't phosphorus have d functions in 6-31G, while atoms such as= potassium and calcium do?  (See, for example, https://www.basissetexchange.org/basis/6-31g/format/gaussian94/?version=3D1= &elements=3D19,20 .)  I realize that phosphorus ([Ne] 3s^2 3p^= 3) doesn't have d electrons, but neither do potassium ([Ar] 4s^1) or calciu= m ([Ar] 4s^2) and yet their 6-31G basis functions do include d functions ([Ar] =3D [Ne] 3s^2 3p^6 and [Ne] =3D 1s^2 2s^2 2p^= 6). 

 

Thanks so much for your help, and thanks for your pa= tience with a probably very basic question,

Andrew

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