Aims. Cataclysmic variables (CVs) are compact binary systems in which a white dwarf accretes matter from a Roche-lobe-filling companion star. For this study we searched for new CVs in the Milky Way in the Chandra Source Catalog v2.0, cross-matched with Gaia Data Release 3 (DR3). Methods. We identified new CV candidates by combining X-ray and optical data in a color-color diagram called the X-ray main sequence. We used two different cuts in this diagram to compile pure and optically variable samples of CV candidates. We undertook optical spectroscopic follow-up observations with the Keck and Palomar Observatories to confirm the nature of these sources. Results. We assembled a sample of 25 887 Galactic X-ray sources and found 14 new CV candidates. Seven objects show X-ray and/or optical variability. All sources show X-ray luminosity in the 1029 − 1032 erg s−1 range, and their X-ray spectra can be approximated by a power-law model with photon indices in the Γ ∼ 1 − 3 range or an optically thin thermal emission model in the kT ∼ 1 − 70 keV range. We spectroscopically confirmed four CVs, discovering two new polars, one low accretion rate polar and a WZ Sge-like low accretion rate CV. X-ray and optical properties of the other nine objects suggest that they are also CVs (likely magnetic or dwarf novae), and one other object could be an eclipsing binary, but revealing their true nature requires further observations. Conclusions. These results show that a joint X-ray and optical analysis can be a powerful tool for finding new CVs in large X-ray and optical catalogs. X-ray observations such as those by Chandra are particularly efficient at discovering magnetic and low accretion rate CVs, which could be missed by purely optical surveys.
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