$X\rightarrow B$ | 20 | $\Delta_{2,1^{\prime}}=-1.4$ | $\sigma^{+}$
Table 19: Parameters used for MOT simulations in Fig. 15. Detunings
$\Delta_{HF}$ are indexed relative to the indicated X${}^{2}\Sigma$ hyperfine
level (see Fig. 15(a)). Bold font indicates levels that participate in a dual-
frequency scheme (on $|F=2,J=3/2\rangle$).  Figure 15: Results of OBE
simulations for the MOT configurations indicated in Table 19 for CaF.
Similarly to in SrF, we see enhanced trapping and cooling in the two-color
MOTs that were tested.

## References

## References

  * [1] J. F. Barry, D. J. McCarron, E. B. Norrgard, M. H. Steinecker, and D. DeMille.  Magneto-optical trapping of a diatomic molecule.  Nature, 512:286, 2014.
  * [2] L. Anderegg, B. L. Augenbraun, E. Chae, B. Hemmerling, N. R. Hutzler, A. Ravi, A. Collopy, J. Ye, W. Ketterle, and J. M. Doyle.  Radio frequency magneto-optical trapping of CaF with high density.  Phys. Rev. Lett., 119:103201, 2017.
  * [3] S. Truppe, H. J. Williams, M. Hambach, L. Caldwell, N. J. Fitch, E. A. Hinds, B. E. Sauer, and M. R. Tarbutt.  Molecules cooled below the doppler limit.  Nature Phys., 13:1173, 2017.
  * [4] A. L. Callopy, S. Ding, Y. Wu, I. A. Finneran, L. Anderegg, B. L. Augenbraun, J. M. Doyle, and J. Ye.  3D magneto-optical trap of yttrium monoxide.  Phys. Rev. Lett., 121:213201, 2018.
  * [5] N. B. Vilas, C. Hallas, L. Anderegg, P. Robichaud, A. Winnicki, D. Mitra, and J. M. Doyle.  Magneto-optical trapping and sub-doppler cooling of a polyatomic molecule.  Nature, 606:70, 2022.
  * [6] K. K. Ni, S. Ospelkaus, M. H. G. de Miranda, A. Pe’er, B. Neyenhuis, J. J. Zirbel, S. Kotochigova, P. S. Julienne, D. S. Jin, and J. Ye.  A high phase-space-density gas of polar molecules.  Science, 322:231, 2008.
  * [7] P. K. Molony, P. D. Gregory, Z. Ji, B. Lu, M. P. Köppinger, C. Ruth Le Sueur, C. L. Blackley, J. M. Hutson, and S. L. Cornish.  Creation of ultracold 87Rb133Cs molecules in the rovibrational ground state.  Phys. Rev. Lett., 113:255301, 2014.
  * [8] M. Guo, B. Zhu, B. Lu, X. Ye, F. Wang, R. Vexiau, N. Bouloufa-Maafa, G. Quéméner, O. Dulieu, and D. Wang.  Creation of an ultracold gas of ground-state dipolar 23Na87Rb molecules.  Phys. Rev. Lett., 116:205303, 2016.
  * [9] J. Woo Park, S. A. Will, and M. W. Zwierlein.  Ultracold dipolar gas of fermionic 23Na40K molecules in their absolute ground state.  Phys. Rev. Lett., 114:205302, 2015.
  * [10] A. Ridinger, S. Chaudhuri, T. Salez, U. Eismann, D. R. Fernandes, K. Magalhaes and. D Wilkowski, C. Salomon, and F. Chevy.  Large atom number dual-species magneto-optical trap for fermionic 6li and 40k atoms.  Eur. Phys J. D, 65:223, 2011.
  * [11] N. Radwell, G. Walker, and S. Franke-Arnold.  Cold-atom densities of more than $10^{12}$cm-3 in a holographically shaped dark spontaneous-force optical trap.  Phys. Rev. A., 88:043409, 2013.
  * [12] K. N. Jarvis, J. A. Devlin, T. E. Wall, B. E. Sauer, and M. R. Tarbutt.  Blue-detuned magneto-optical trap.  Phys. Rev. Lett., 120:083201, 2018.
  * [13] L. W. Cheuk, L. Anderegg, B. L. Augenbraun, Y. Bao, S. Burchesky, W. Ketterle, and J. M. Doyle.  $\Lambda$-enhanced imaging of molecules in an optical trap.  Phys. Rev. Lett., 121:083201, 2018.
  * [14] T. K. Langin, V. Jorapur, Y. Zhu, Q. Wang, and D. DeMille.  Polarization enhanced deep optical dipole trapping of $\Lambda-$cooled polar molecules.  Phys. Rev. Lett., 127:163201, 2021.
  * [15] Y. Wu, J. J. Burau, K. Mehling, J. Ye, and S. Ding.  High phase-space density of laser-cooled molecules in an optical lattice.  Phys. Rev. Lett., 127:263201, 2021.
  * [16] Y. Lu, C. M. Holland, and L. W. Cheuk.  Molecular laser cooling in a dynamically tunable repulsive optical trap.  Phys. Rev. Lett., 128:213201, 2022.
  * [17] C. Hallas, N. B. Vilas, L. Anderegg, P. Robichaud, A. Winnicki, C. Zhang, L. Cheng, and J. M. Doyle.  Optical trapping of a polyatomic molecule in an l-type parity doublet state.  arXiv:2208.13762, 2022.
  * [18] G. Valtolina, K. Matsuda, W. Tobias, J. R. Li, L. De Marco, and J. Ye.  Dipolar evaporation of reactive molecules to below the fermi temperature.  Nature, 588:239, 2020.
  * [19] J. Li, W. G. Tobias, K. Matsuda, C. Miller, G. Valotlina, L. De Marco, R. Wang, L. Lassabliere, G. Quemener, J. L. Bohn, and J. Ye.  Tuning of dipolar interactions and evaporative cooling in a three-dimensional molecular quantum gas.  Nature Phys., 17:1144, 2021.
  * [20] A. Schindewolf, R. Bause, X. Chen, M. Duda, T. Karman, I. Bloch, and X. Luo.  Evaporation of microwave-shielded polar molecules to quantum degeneracy.  Nature, 607:677, 2022.
  * [21] Z. Idziaszek and P. S. Julienne.  Universal rate constants for reactive collisions of ultracold molecules.  Phys. Rev. Lett., 104:113202, 2010.
  * [22] L. W. Cheuk, L. Anderegg, Y. Bao, S. Burchesky, S. Yu, W. Ketterle, K. K. Ni, and J. M. Doyle.  Observation of collisions between two ultracold ground-state CaF molecules.  Phys. Rev. Lett., 125:043401, 2020.
  * [23] L. Anderegg, S. Burchesky, Y. Bao, S. Yu, T. Karman, E. Chae, K. K. Ni, W. Ketterle, and J. M. Doyle.  Observation of microwave shielding of ultracold molecules.  Science, 373:779, 2021.
  * [24] N. Vanhaecke and O. Dulieu.  Precision measurements with polar molecules: the role of the black body radiation.  Molecular Physics, 105:1723, 2007.
  * [25] J. A. Devlin and M. R. Tarbutt.  Three-dimensional doppler, polarization-gradient, and magneto-optical forces for atoms and molecules with dark states.  New J. Phys., 18:123017, 2016.
  * [26] J. A. Devlin and M. R. Tarbutt.  Laser cooling and magneto-optical trapping of molecules analyzed using optical bloch equations and the fokker-planck-kramers equation.  Phys. Rev. A., 98:063415, 2018.
  * [27] L. R. Hunter, S. K. Peck, A. S. Greenspon, S. S. Alam, and D. DeMille.  Prospects for laser cooling tlf.  Phys. Rev. A., 85:012511, 2012.
  * [28] S. Truppe, S. Marx, S. Kray, M. Doppelbauer, S. Hofsass, H. C. Schewe, N. Walter, J. Perez-Rios, B. G. Sartakov, and G. Meijer.  Spectroscopic characterization of aluminum monofluoride with relevance to laser cooling and trapping.  Phys. Rev. A., 100:052513, 2019.
  * [29] J. R. Daniel, C. Wang, K. Rodriguez, B. Hemmerling, T. N. Lewis, C. Bardeen, A. Teplukhin, and B. K. Kendrick.  Spectroscopy on the A${}^{1}\Pi\leftarrow$X${}^{1}\Sigma^{+}$ transition of buffer-gas-cooled alcl.  Phys. Rev. A., 104:012801, 2021.
  * [30] J. C. Shaw, S. Hannig, and D. J. McCarron.  Stable 2 w continuous-wave 261.5 nm laser for cooling and trapping aluminum monochloride.  Optics Express, 29:37140, 2021.
  * [31] M. D. Di Rosa.  Laser-cooling molecules.  European Physical Journal D, 31:395, 2004.
  * [32] E. S. Shuman, J. F. Barry, and D. DeMille.  Laser cooling of a diatomic molecule.  Nature, 467:820, 2010.
  * [33] W. J. Childs, L. S. Goodman, and I. Renhorn.  Radio-frequency optical double-resonance spectrum of srf: The X${}^{2}\Sigma^{+}$ state.  Journal of Molecular Spectroscopy, 87:522, 1981.
  * [34] W. J. Childs, G. L. Goodman, and L. S. Goodman.  Precise determination of the v and n dependence of the spin-rotation and hyperfine interactions in the caf ground state.  Journal of Molecular Spectroscopy, 87:365, 1981.
  * [35] J. M. Brown and A. Carrington.  Rotational spectroscopy of diatomic molecules.  Cambridge Univ. Press, Cambridge, United Kingdom, 2003.
  * [36] B. E. Sauer, J. Wang, and E. A. Hinds.  Laser-rf double resonance spectroscopy of 174ybf in the x${}^{2}\Sigma^{+}$ state: Spin-rotation, hyperfine interactions, and the electric dipole moment.  J. Chem. Phys., 105:7412, 1996.
  * [37] P. J. Dagdigian, H. W. Cruse, and R. N. Zare.  Radiative lifetimes of the alkaline earth monohalides.  J. Chem. Phys., 60:2330, 1974.
  * [38] J. Nakagawa, R. F. Wormsbecher, and D. O. Harris.  High-resolution laser excitation spectra of linear triatomic molecules: Analysis of the B${}^{2}\Sigma^{+}-$X${}^{2}\Sigma^{+}$ system of sroh and srod.  Journal of Molecular Spectroscopy, 97:37, 1983.
  * [39] H. J. Metcalf and P. van der Straten.  Laser Cooling and Trapping.  Springer Science & Business Media, New York City, United States, 1999\.
  * [40] T. E. Wall, J. F. Kanem, J. J. Hudson, B. E. Sauer, D. Cho, M. G. Boshier, E. A. Hinds, and M. R. Tarbutt.  Lifetime of the $A(v^{\prime}=0)$ state and Franck-Condon factor of the $A-X(0-0)$ transition of CaF measured by the saturation of laser-induced fluorescence.  Phys. Rev. A., 78:062509, 2008.
  * [41] T. C. Steimle, P. J. Domaille, and D. O. Harris.  Rotational analysis of the B${}^{2}\Sigma^{+}-$X${}^{2}\Sigma^{+}$ system of srf using a cw tunable dye laser.  Journal of Molecular Spectroscopy, 68:134, 1977.
  * [42] I. Kozyryev, L. Baum, K. Matsuda, P. Olson, B. Hemmerling, and J. M. Doyle.  Collisional relaxation of vibrational states of sroh with he at 2 k.  New J. Phys., 17:045003, 2015.
  * [43] I. Kozyryev, T. C. Steimle, P. Yu, D. Nguyen, and J. M. Doyle.  Determination of caoh and caoch3 vibrational branching ratios for direct laser cooling and trapping.  New J. Phys., 21:052002, 2019.
  * [44] J. Gu, Z. Xiao, C. Yu, Q. Zhang, Y. Chen, and D. Zhao.  High resolution laser excitation spectra and franck-condon factors of A${}^{2}\Pi-$X${}^{2}\Sigma^{+}$ electronic transition of mgf.  Chinese Journal of Chemical Physics, 35:58, 2022.
  * [45] M. R. Tarbutt.  Magneto-optical trapping forces for atoms and molecules with complex level structures.  New J. Phys., 17:015007, 2015.
  * [46] M. R. Tarbutt and T. C. Steimle.  Modeling magneto-optical trapping of caf molecules.  Phys. Rev. A., 92:053401, 2015.
  * [47] M. T. Hummon, M. Yeo, B. K. Stuhl, A. L. Collopy, Y. Xia, and J. Ye.  2d magneto-optical trapping of diatomic molecules.  Phys. Rev. Lett., 110:143001, 2013.
  * [48] E. B. Norrgard, D. J. McCarron, M. H. Steinecker, M. R. Tarbutt, and D. DeMille.  Submillikelvin dipolar molecules in a radio-frequency magneto-optical trap.  Phys. Rev. Lett., 116:063004, 2016.
  * [49] W. D. Phillips and H. Metcalf.  Laser deceleration of an atomic beam.  Phys. Rev. Lett., 48:596, 1982.
  * [50] M. Petzold, P. Kaebert, P. Gersema, M. Siercke, and S. Ospelkaus.  A zeeman slower for diatomic molecules.  New J. Phys., 20:042001, 2018.
  * [51] M. Petzold, P. Kaebert, P. Gersema, T. Poll, N. Reinhardt, M. Siercke, and S. Ospelkaus.  Type-ii zeeman slowing: Characterization and comparison to conventional radiative beam-slowing schemes.  Phys. Rev. A., 98:063408, 2018.
  * [52] Q. Liang, W. Bu, Y. Zhang, T. Chen, and B. Yan.  Improvements on type-ii zeeman slowing of molecules through polarization selectivity.  Phys. Rev. A., 100:053402, 2019.
  * [53] J. Dalibard and C. Cohen-Tannoudji.  Laser cooling below the doppler limit by polarization gradients: simple theoretical models.  J. Opt. Soc. Am. B, 6:2023, 1989.
  * [54] P. D. Lett, R. N. Watts, C. I. Westbrook, W. D. Phillips, P. L. Gould, and H. J. Metcalf.  Observation of atoms laser cooled below the doppler limit.  Phys. Rev. Lett., 61:169, 1988.
  * [55] P. J. Ungar, D. S. Weiss, E. Riis, and S. Chu.  Optical molasses and multilevel atoms: theory.  J. Opt. Soc. Am. B, 6:2058, 1989.
  * [56] M. Weidemuller, T. Esslinger, M. A. Ol’shanii, A. Hemmerich, and T. W. Hansch.  A novel scheme for efficient cooling below the photon recoil limit.  Europhysics Letters, 27:109, 1994.
  * [57] K. N. Jarvis, B. E. Sauer, and M. R. Tarbutt.  Characteristics of unconventional rb magneto-optical traps.  Phys. Rev. A., 98:043432, 2018.
  * [58] A. T. Grier, I. Ferrier-Barbut, B. S. Rem, M. Delehaye, L. Khaykovich, F. Chevy, and C. Salomon.  $\Lambda$-enhanced sub-doppler cooling of lithium atoms in D1 gray molasses.  Phys. Rev. A., 87:063411, 2013.
  * [59] F. Sievers, N. Kretzschmar, D. Rio Fernandes, D. Suchet, M. Rabinovic, S. Wu, C. V. Parker, L. Khaykovich, C. Salomon, and F. Chevy.  Simultaneous sub-doppler laser cooling of fermionic 6Li and 40K on the D1 line: Theory and experiment.  Phys. Rev. A., 91:023426, 2015.
  * [60] S. Rosi, A. Burchianti, S. Conclave, D. S. Naik, G. Roati, C. Fort, and F. Minardi.  $\Lambda$-enhanced grey molasses on the D2 transition of rubidium-87 atoms.  Scientific Reports, 8:1301, 2018.
  * [61] A. Burchianti, G. Valtolina, J. A. Seman, E. Pace, M. De Pas, M. Inguscio, M. Zaccanti, and G. Roati.  Efficient all-optical production of large 6Li quantum gases using D1 gray-molasses cooling.  Phys. Rev. A., 90:043408, 2014.
  * [62] G. Salomon, L. Fouche, P. Want, A. Aspect, P. Pouyer, and T. Bourdel.  Gray-molasses cooling of 39K to a high phase-space density.  EPL, 104:63002, 2013.
  * [63] S. Ding, Y. Wu, I. A. Finneran, J. J. Burau, and Jun Ye.  Sub-doppler cooling and compressed trapping of YO molecules at $\mu$K temperatures.  Phys. Rev. X., 10:021049, 2020.
  * [64] L. Caldwell, J. A. Devlin, H. J. Williams, N. J. Fitch, E. A. Hinds, B. E. Sauer, and M. R. Tarbutt.  Deep laser cooling and efficient magnetic compression of molecules.  Phys. Rev. Lett., 123:033202, 2019.
  * [65] J. F. Barry, E. S. Shuman, and D. DeMille.  A bright, slow cryogenic molecular beam source for free radicals.  Phys. Chem. Chem. Phys., 13:18936, 2011.
  * [66] N. R. Hutzler, H. Lu, and J. M. Doyle.  The buffer gas beam: An intense, cold, and slow source for atoms and molecules.  Chem. Rev., 112:4803, 2012.
  * [67] J. A. Gordon and A. Ashkin.  Motion of atoms in a radiation trap.  Phys. Rev. A., 21:1606, 1979.
  * [68] J. Bezanson, A. Edelman, S. Karpinski, and V. B. Shah.  Julia: A fresh approach to numerical computing.  SIAM review, 59(1):65–98, 2017.
  * [69] V. I. Yudin, A. V. Taichenachev, and M. Yu. Basalaev.  Dynamic steady state of periodically driven quantum systems.  Phys. Rev. A., 93:013820, 2016.
  * [70] S. Xu, P. Kaebert, M. Stepanova, T. Poll, M. Siercke, and S. Ospelkaus.  Maximizing the capture velocity of molecular magneto-optical traps with bayesian optimizations.  New J. Phys., 23:063062, 2021.
  * [71] S. Xu, P. Kaebert, M. Stepanova, T. Poll, M. Siercke, and S. Ospelkaus.  Engineering the sub-doppler force in molecular magneto-optical traps.  arXiv:2203.07754.
  * [72] M. Walhout, J. Dalibard, S. L. Rolston, and W. D. Phillips.  $\sigma_{+}-\sigma_{-}$ optical molasses in a longitudinal magnetic field.  J. Opt. Soc. Am. B, 9:1997, 1992.
  * [73] M. H. Steinecker, D. J. McCarron, Y. Zhu, and D. DeMille.  Improved radio‐frequency magneto‐optical trap of srf molecules.  ChemPhysChem, 17:3664, 2016.
  * [74] L. Anderegg, B. L. Augenbraun, Y. Bao, S. Burchesky, L. W. Cheuk, W. Ketterle, and J. M. Doyle.  Laser cooling of optically trapped molecules.  Nature Phys., 14:890, 2018.
  * [75] I. Kozyryev, L. Baum, K. Matsuda, B. L. Augenbraun, L. Anderegg, A. P. Sedlack, and J. M. Doyle.  Sisyphus laser cooling of a polyatomic molecule.  Phys. Rev. Lett., 118:173201, 2017.
  * [76] L. Baum, N. B. Vilas, C. Hallas, B. L. Augenbraun, S. Raval, D. Mitra, and J. M. Doyle.  1d magneto-optical trap of polyatomic molecules.  Phys. Rev. Lett., 124:133201, 2020.
  * [77] Z. Lasner, A. Lunstad, C. Zhang, L. Cheng, and J. M. Doyle.  Vibronic branching ratios for nearly closed rapid photon cycling of sroh.  Phys. Rev. A., 106:L020801, 2022.
  * [78] S. Kang, Y. Gao, F. Kuang, T. Gao, J. Du, and G. Jiang.  Theoretical study of laser cooling of magnesium monofluoride using ab initio methods.  Phys. Rev. A., 91:042511, 2015.
  * [79] L. Xu, Y. Yin, B. Wei, Y. Xia, and J. Yin.  Calculation of vibrational branching ratios and hyperfine structure of 24Mg19F and its suitability for laser cooling and magneto-optical trapping.  Phys. Rev. A., 93:013408, 2016.
  * [80] S. Xu, M. Xia, Y. Yin, R. Gu, Y. Xia, and J. Yin.  Determination of the normal A${}^{2}\Pi$ state in mgf with application to direct laser cooling of molecules.  J. Chem. Phys., 150:084302, 2019.
  * [81] M. Doppelbauer, S. C. Wright, S. Hofsass, B. G. Sartakov, G. Meijer, and S. Truppe.  Hyperfine-resolved optical spectroscopy of the A${}^{2}\Pi\leftarrow$ X${}^{2}\Sigma^{+}$ transition in mgf.  J. Chem. Phys., 156:134301, 2022.
  * [82] J. F. Barry, E. S. Shuman, E. B. Norrgard, and D. DeMille.  Laser radiation pressure slowing of a molecular beam.  Phys. Rev. Lett., 108:103002, 2012.
  * [83] S. Truppe, H. J. Williams, N. J. Fitch, M. Hambach, T. E. Wall, E. A. Hinds, B. E. Sauer, and M. R. Tarbutt.  An intense, cold, velocity-controlled molecular beam by frequency-chirped laser slowing.  New J. Phys., 19:022001, 2017.
  * [84] K. Dieckmann, R. J. C. Spreeuw, M. Weidemuller, and J. T. M. Walraven.  Two-dimensional magneto-optical trap as a source of slow atoms.  Phys. Rev. A., 58:3891, 1998.
  * [85] X. Alauze, J. Lim, M. A. Trigatzis, S. Swarbrick, N. J. Collings, B. E. Sauer, and M. R. Tarbutt.  An ultracold molecular beam for testing fundamental physics.  Quantum Sci. Technol., 6:044005, 2021.
  * [86] P. S. Julienne, T. M. Hanna, and Z. Idziaszek.  Universal ultracold collision rates for polar molecules of two alkali-metal atoms.  Phys. Chem. Chem. Phys., 13:19114, 2011.
  * [87] L. Lassabliere and G. Quemener.  Controlling the scattering length of ultracold dipolar molecules.  Phys. Rev. Lett., 121:163402, 2018.
  * [88] T. Karman and J. M. Hutson.  Microwave shielding of ultracold polar molecules.  Phys. Rev. Lett., 121:163401, 2018.
  * [89] A. Micheli, G. K. Brennen, and P. Zoller.  A toolbox for lattice-spin models with polar molecules.  Nature Phys., 2:341, 2006.
  * [90] M. V. Ivanov, F. H. Bangerter, P. Wojcik, and A. I. Krylov.  Toward ultracold organic chemistry: Prospects of laser cooling large organic molecules.  J. Phys. Chem. Lett, 11:6670, 2020.
  * [91] B. L. Augenbraun, J. M. Doyle, T. Zelevinsky, and I. Kozyryev.  Molecular asymmetry and optical cycling: Laser cooling asymmetric top molecules.  Phys. Rev. X., 10:031022, 2020.
  * [92] D. Mitra, Z. D. Lasner, G. Zhu, C. E. Dickerson, B. L. Augenbraun, A. D. Bailey, A. N. Alexandrova, W. C. Campbell, J. R. Caram, E. R. Hudson, and J. M. Doyle.  Pathway toward optical cycling and laser cooling of functionalized arenes.  J. Phys. Chem. Lett., 13:7029, 2022.
  * [93] J. Lim, J. R. Almond, M. A. Trigatzis, J. A. Devlin, N. J. Fitch, B. E. Sauer, M. R. Tarbutt, and E. A. Hinds.  Laser cooled YbF molecules for measuring the electron’s electric dipole moment.  Phys. Rev. Lett., 120:123201, 2018.
  * [94] B. L. Augenbraun, Z. D. Lasner, A. Frenett, H. Sawaoka, C. Miller, T. C. Steimle, and J. M. Doyle.  Laser-cooled polyatomic molecules for improved electron electric dipole moment searches.  New J. Phys., 22:022003, 2020.
  * [95] I. Koyryev and N. R. Hutler.  Precision measurement of time-reversal symmetry violation with laser-cooled polyatomic molecules.  Phys. Rev. Lett., 119:133002, 2017.
  * [96] The NL eEDM collaboration.  Measuring the electric dipole moment of the electron in baf.  Eur. Phys. J. D, 72:197, 2018.
  * [97] J. Devlin, M. R. Tarbutt, D. L. Kokkin, and T. C. Steimle.  Measurements of the zeeman effect in the A${}^{2}\Pi$ and B${}^{2}\Sigma^{+}$ states of calcium fluoride.  Journal of Molecular Spectroscopy, 317:1, 2015.
  * [98] R. F. Curl.  The relationship between electron spin rotation coupling constants and g-tensor components.  Molecular Physics, 9:6:589, 1965.