Appendix J Phase convention of real spherical harmonics

In quantum chemistry applications, an Condon-Shortley phase can be added to the real spherical harmonics (RSH) based on the developers’ choice.

If, the commonly used Condon-Shortley phase is added to the RSH, the definition of RSH becomes

Ylm={(−1)m⁢2⁢Klm⁢cos⁡(m⁢ϕ)⁢Plm⁢(cos⁡θ),m>0(−1)m⁢2⁢Klm⁢sin⁡(|m|⁢ϕ)⁢Pl|m|⁢(cos⁡θ),m<0Klm⁢Plm⁢(cos⁡θ),m=0 (J.4)

where Plm is the associated Legendre polynomials without the Condon-Shortley phase

Plm⁢(cos⁡θ)=(sin⁡θ)m⁢dmd⁢(cos⁡θ)m⁢(Pl⁢(cos⁡θ)), (J.5)

and the coefficient

Klm=(2⁢l+1)⁢(l−|m|)!4⁢π⁢(l+|m|)! (J.6)

The RSH in the FHI-aims code adopt a partly Condon-Shortley phase. Thus, the definition of RSH becomes

Ylm={(−1)m⁢2⁢Klm⁢cos⁡(m⁢ϕ)⁢Plm⁢(cos⁡θ),m>02⁢Klm⁢sin⁡(|m|⁢ϕ)⁢Pl|m|⁢(cos⁡θ),m<0Klm⁢Plm⁢(cos⁡θ),m=0 (J.10)

The code related to these definition can be found in file basis_sets/increment_ylm_original.f90 or basis_sets/SHEval.f90. In some subroutines, the real spherical harmonics are generated using external/ylm_real.f90. The definition of RSH therein seems a bit different

Ylm={2⁢Re⁢Y~lm,m>0−2⁢Im⁢Y~lm,m<0Y~lm,m=0 (J.14)

where Y~lm is the complex spherical harmonics (CSH)

Y~lm⁢(θ,ϕ)=(−1)m⁢2⁢l+14⁢π⁢(l−m)!(l+m)!⁢Plm⁢(cos⁡θ)⁢ei⁢m⁢ϕ (J.15)

It can be shown that the two conventions are equivalent. it is trivial for m=0. For m>0,

(−1)m⁢2⁢Klm⁢cos⁡(m⁢ϕ)⁢Plm⁢(cos⁡θ)= (−1)m⁢2⁢Re⁢[ei⁢m⁢ϕ]⁢Klm⁢Plm⁢(cos⁡θ)
= 2⁢Re⁢[(−1)m⁢ei⁢m⁢ϕ⁢Klm⁢Plm⁢(cos⁡θ)]
= 2⁢Re⁢Y~lm

For m<0

2⁢Klm⁢sin⁡(|m|⁢ϕ)⁢Pl|m|⁢(cos⁡θ)
= 2⁢Im⁢[ei⁢|m|⁢ϕ]⁢Klm⁢Pl|m|⁢(cos⁡θ)
= 2⁢Im⁢[−ei⁢m⁢ϕ]⁢(2⁢l+1)⁢(l+m)!4⁢π⁢(l−m)!⁢Pl−m⁢(cos⁡θ)
= −2⁢Im⁢[ei⁢m⁢ϕ⁢(2⁢l+1)⁢(l−m)!4⁢π⁢(l+m)!⁢(−1)m⁢Plm⁢(cos⁡θ)]
= −2⁢Im⁢Y~lm

where in the third equality we have used the following property

Pl−m=(−1)m⁢(l−m)!(l+m)!⁢Plm. (J.16)

With the property of CSH

Y~l−m=(−1)m⁢Y~lm⁣∗, (J.17)

we can derive another equivalent expression from Eq. (J.14)

Ylm={12⁢[Y~lm+(−1)m⁢Y~l−m],m>0i2⁢[Y~lm−(−1)m⁢Y~l−m],m<0Y~lm,m=0 (J.21)

leading to the representation matrix of FHI-aims RSH in CSH. This can be useful to connect between RSHs from FHI-aims and other codes.